Use Of A Combination Chain Transfer And Activating Agent To Control Molecular Weight And Optical Density Of Pd Catalyzed Norbornene Polymers

ABSTRACT

A method of controlling the molecular weight of poly(cyclic) olefin (norbornene-type) polymers and activating the polymerization thereof with a single material is provided. Such method include adding a chain transfer/activating agent to a mixture of monomer(s), catalyst, solvent and an optional cocatalyst and polymerizing the mixture to form a polymer. It is shown that the amount of chain transfer/activating agent in the mixture can serve to control the molecular weight of the resulting polymer, its percent conversion or both, and in some embodiments the optical density of the resulting polymer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority from U.S. ProvisionalPatent Ser. No. 60/921,066, filed Mar. 30, 2007, and U.S. ProvisionalPatent Ser. No. 60/993,866, filed Sep. 14, 2007, both of which areincorporated herein by reference.

TECHNICAL FIELD

The present invention relates generally to poly(cyclic) olefin polymersand more particularly to, norbornene-type polymers prepared with a chaintransfer/activating agent for controlling molecular weight providingappropriately low optical densities and uses of such polymers.

BACKGROUND

Poly(cyclic) olefin polymers, such as those including norbornene-typerepeating unit structures, have shown promise for use in photoresistcompositions suitable for exposure at wavelengths such as 193 nm and 157nm. For example, positive acting (positive tone) photoresistsencompassing norbornene-type polymers have shown high dissolution ratesafter image-wise exposure and post-exposure thermal treatment, as wellas superior resistance to dry etch and other typical semiconductorprocessing steps and acceptably low optical densities at theaforementioned wavelengths.

It is generally known that low molecular weight polymers, such as thoseused for photoresist compositions, tend to exhibit higher dissolutionrates than their higher molecular weight analogs. Unfortunately, it isalso known that such low molecular weight materials generally have ahigher optical density (OD) than their higher molecular weight analogs.(See, Barclay et al. Macromolecules 1998, 31, 1024 for a discussion ofthese issues for poly(4-hydroxystyrene), the preferred material for 248nm photoresists.) As a result, it is often necessary for a persondesigning such a polymer to target a higher molecular weight thandesired for an optimal dissolution rate so that an acceptable OD can beobtained. It follows then that this compromise between optimaldissolution rate and optimal OD results in a photoresist compositionthat is not optimized for either characteristic.

While optically transparent dissolution rate modifiers (DRMs), amaterial that can be added to the photoresist composition to enhance thedissolution rate in appropriate areas of the resist and the use of anolefinic chain transfer agent (CTA) during the forming of a polymer canprovide for acceptable dissolution rates, DRMs increase both thecomplexity of the resist composition and its cost, while olefinic CTAshave been found to provide acceptably low molecular weight polymers withhigher than desirable ODs.

In U.S. Published Application 2004/0229157, non-olefinic chain transferagents, such as hydrogen and some alkyl silanes, are described. Whileboth types of CTAs can successfully control the molecular weight ofnorbornene-type polymers while not resulting in increased opticaldensity, hydrogen's flammability and the need to remove silane residuesfrom the polymer product where alkyl silanes are employed can at timesbe problematic.

Therefore, it would be desirable to find alternative methods ofproviding controllably low molecular weight polymers that do notencompass the above-mentioned deficiencies and/or problems whileproviding for norbornene-type polymers having both controllablemolecular weight and appropriately low ODs. Further such alternatemethods should not result in an unacceptable reduction in the conversionrate of the polymerization as compared to previously described CTAs.Still further, such alternate methods should not inappropriatelyincrease the complexity of the process or the cost of the resultingpolymer.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 shows a schematic of a theoretical polymerization mechanism ofembodiments of the present invention.

DETAILED DESCRIPTION

Embodiments in accordance with the present invention are directed toproviding methods of forming polycyclic olefin polymers, such asnorbornene-type polymers, with both controllable molecular weight anddesirably low optical density. Some embodiments in accordance with thepresent invention are further directed to providing such methods andpolymers where essentially phosphorus-free polymerization catalysts areemployed.

Unless otherwise indicated, all numbers, values and/or expressionsreferring to quantities of ingredients, reaction conditions, etc., usedherein are to be understood as modified in all instances by the term“about” as absent the aforementioned indication, such numbers areapproximations reflective of, among other things, the variousuncertainties of measurement encountered in obtaining such values.Further, where a numerical range is disclosed herein such range iscontinuous, and includes every value between the minimum and maximumvalues of such range. Still further, where a range refers to integers,every integer between the minimum and maximum values of such range isincluded.

As used herein, the term “polymer composition” is meant to include asynthesized polymer, as well as residues from initiators, catalysts andother elements attendant to the synthesis of such polymer, where suchresidues are understood as not being covalently incorporated thereto.Such residues and other elements considered as part of the polymercomposition are typically mixed or co-mingled with the polymer such thatthey tend to remain with the polymer when it is transferred betweenvessels or between solvent or dispersion media. A polymer compositioncan also include materials added after synthesis of the polymer toprovide or modify specific properties to such composition.

As used herein, “hydrocarbyl” refers to a radical of a group thatcontains only carbon and hydrogen, non-limiting examples being alkyl,cycloalkyl, aryl, aralkyl, alkaryl, and alkenyl. The term“halohydrocarbyl” refers to a hydrocarbyl group where at least onehydrogen has been replaced by a halogen. The term perhalocarbyl refersto a hydrocarbyl group where all of the hydrogens have been replaced bya halogen.

As used herein, “alkyl” refers to a linear or branched acyclic orcyclic, saturated hydrocarbon group having a carbon chain length of, forexample, from C₁ to C₂₅. Non-limiting examples of suitable alkyl groupsinclude, but are not limited to, —(CH₂)₃CH₃, —(CH₂)₄CH₃, —(CH₂)₅CH₃,—(CH₂)₁₀CH₃, —(CH₂)₂₃CH₃ and cyclohexyl. The term “alkylol” refers toalkyl groups that include one or more hydroxyl groups.

As used herein the term “aryl” refers to aromatic groups that include,without limitation, groups such as phenyl, biphenyl, benzyl, xylyl,naphthalenyl, anthracenyl and the like, as well as heterocyclic aromaticgroups that include, without limitation, pyridinyl, pyrrolyl, furanyl,thiophenyl and the like.

As used herein the terms “alkaryl” or “aralkyl” refer to a linear orbranched acyclic alkyl group substituted with at least one aryl group,for example, phenyl, and having an alkyl carbon chain length of C₂ toC₂₅. The aryl group can be further substituted, if desired. Non-limitingexamples of suitable substituent groups for the aryl group include,among others, hydroxyl groups, benzyl groups, carboxylic acid andcarboxylic acid ester groups and aliphatic hydrocarbon groups. The alkylgroup can be substituted with halogens.

As used herein, “alkenyl” refers to a linear or branched acyclic orcyclic hydrocarbon group having one or more double bonds and having analkenyl carbon chain length of C₂ to C₂₅.

It will be understood that in the context of this disclosure, the term“low molecular weight” should be taken to mean a polymer with amolecular weight of less than about 20,000. It will also be understoodthat the term “low optical density” (low OD) should be taken to mean anoptical density (OD) at 193 nm of less than about 0.25.

Additionally, it will be understood that in the context of thisdisclosure, the terms “non-phosphorous containing” or “phosphorous-free”when used to describe palladium catalysts, also include such catalyststhat do not encompass arsenic (As), stilbene (Sb) or bismuth (Bi).

Methods in accordance with the present invention encompass combining oneor more poly(cyclic) olefin monomers, a palladium catalyst, and a chaintransfer/activating agent (CTAA) to form a mixture; and causing suchmixture to polymerize thus forming a desired polymer. In someembodiments, such palladium catalyst is a non-phosphorus containingpalladium catalyst. Advantageously, it has been found that the CTAAsemployed in such embodiments can both control the molecular weight ofthe resultant polymer via a chain termination step and serve as acatalyst activating agent. As will be later shown, optimizing thereaction conditions (i.e., temperature, time, amount of CTAA added) canproduce low molecular weight polymers with a generally high conversionrate as compared to an agent capable only of chain transfer and in someembodiments, advantageously provide polymers with a desirably lowoptical density (OD).

Without wishing to be bound to any particular theory, it is believedthat a proposed reaction scheme is presented in FIG. 1. For ease ofunderstanding and explanation, the description of FIG. 1 employs formicacid as an exemplary CTAA, palladium acetate as an exemplary catalystand a generic substituted norbornene-type monomer. As shown, it isbelieved that the CTAA promotes the forming of an active palladiumhydride cation PdH⁺ which can participate in one of the two major chaintransfer events that are operative and competing. In the upper half ofthe mechanism, a unimolecular chain transfer event that first involvesinsertion of the norbornene double bond into the Pd—H bond of thecationic PdH. Once formed, this intermediate is believed to be capableof undergoing a rearrangement of the bicyclic system into a monocyclicsystem by β-carbon cleavage of the methylene bridge thus forming anendo-cyclic double bond where the Pd has migrated to the formermethylene bridge carbon as seen in the second intermediate. While priorto this rearrangement the Pd was not beta (β) to readily accessiblehydrogens, in the resulting intermediate, the Pd can freely rotate so asto align itself for H elimination from the β-tertiary carbon shown, toallow for the forming of an exo-cyclic double bond thus terminating thepolymer chain with a diene end group, as depicted. The cationic Pd—Hspecies eliminated should then be available for subsequent chaininitiation. Thus in this upper mechanism β-C cleavage is a prelude tothe β-H chain transfer reaction that serves to terminate a polymer chainduring the polymerization.

In the lower half of the proposed mechanism, a bimolecular chaintransfer event is shown. In this mechanism the intermediate describedabove is again believed to be formed by insertion of the norbornenedouble bond into the Pd—H bond of the PdH⁺, but rather than arearrangement, a bimolecular reaction with the acidic hydrogen of theformic acid CTAA serves to eliminate the Pd as a Pd-formate andterminate the polymer chain with a hydrogen end group, as depicted. Itis believed that this cation can advantageously eliminate CO₂ andre-form the cationic Pd—H species. Thus the formic acid serves to bothinitiate the chain transfer and reform the active Pd—H cation. It shouldbe understood that is the degree to which each of the upper or lowerchain transfer events occur that contributes to the combined molecularweight and optical density lowering of the polymers that result from theuse of a CTAA. That is to say, if the upper mechanism in which diene endgroups are created predominates, a majority of polymer chains having adiene termination will be created while if, by and through the additionof a CTAA such as formic acid, the lower mechanism predominates, amajority of polymer chains will be hydrogen terminated.

Thus CTAAs, in general, are believed to have the necessary properties toterminate the chain of a growing polymer as well as to enable anintermediate catalyst complex to generate an active palladium hydridefor continued chain polymerization. Some embodiments of the presentinvention encompass CTAAs such as formic acid, however while only formicacid embodiments are exemplified hereinafter, it is believed that othersuch acids, for example, thio-formic acid and dithio-formic acid, amongothers, can also perform as CTAAs. Therefore it is not the intent of theinventors to limit the scope and spirit of the present invention toformic acid.

It has been found that the molecular weight of the resulting polymer isrelated, in part, to the concentration of the CTAA, since in mostinstances it is observed that as the CTAA concentration increases, themolecular weight of the resultant poly(norbornene) decreases. However,it is also observed that in some instances certain concentrations ofCTAA produce polymers with unexpectedly high molecular weights. Withoutwishing to be bound by theory, and as shown in FIG. 1, it is believedthat the since both the activation effect and terminating effect of suchagent are created by the same agent such effects are necessarilyrelated. Therefore, it may very well be that at certain concentrationlevels of the CTAA, one effect may predominate over the other. Thus,while the theoretical reaction schemes of FIG. 1 illustrates that theCTAA can be both an activating agent and a chain transfer agent, suchscheme does not address any effects that variations in relativeamount/concentration of the CTAA employed can cause. While thisrelationship will be discussed more fully below and illustrated by theExamples provided hereinafter, it should be understood, that for anypolymerization reaction (the catalyst, CTAA, monomer(s), solvents, etc.)the relative amounts of the several materials provided to the reactionvessel as well as the reaction conditions (time, temperature, etc.)employed can influence the polymer obtained. That is to say, for any setof materials, varying these relative amounts and/or reaction conditionscan readily be used to provide a desired polymer.

It should be further noted that in embodiments of the present inventionwhere a phosphorous-containing catalyst complex is employed, chaintermination to form the diene seems less favored than in embodimentsthat employ a phosphorous-free catalyst complex. While this differencebetween these types of catalysts is not fully understood, it is believedthat where a phosphorous-free complex contains at least one moiety thatis replaceable by one or more CTAA's, a polymerization employing such acomplex will generally provide a polymer having a lower optical densityas the CTAA concentration is increased.

Embodiments in accordance with the present invention are suitable forthe preparation of polymers encompassing a wide range of norbornene-typerepeating units. As defined herein, the terms “polycycloolefin”,“poly(cyclic) olefin”, and “norbornene-type” are used interchangeablyand refer to addition polymerizable monomers (or the resulting repeatingunit), that encompass at least one norbornene moiety such as shownbelow:

The simplest norbornene-type or poly(cyclic) olefin monomer encompassedby embodiments in accordance with the present invention is the bicyclicmonomer, bicyclo[2.2.1]hept-2-ene, commonly referred to as norbornene.However, the term norbornene-type monomer or repeating unit is usedherein to mean norbornene itself as well as any substitutednorbornene(s), or substituted and unsubstituted higher cyclicderivatives thereof. Structural formula A, shown below, isrepresentative of such norbornene monomers:

-   -   where X is selected from —CH₂—, —CH₂—CH₂, O, S, and —NH—; m is        an integer from 0 to 5 and each occurrence of R¹, R², R³ and R⁴        independently represents hydrogen, a hydrocarbyl or other        substituent.

When any of R¹ to R⁴ is a hydrocarbyl group, such group can be a C₁ toC₃₀ alkyl, aryl, aralkyl, alkaryl, alkenyl, alkynyl, cycloalkyl,cycloalkenyl, alkylidenyl or alkylsilyl group. Representative alkylgroups include, but are not limited to, methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl,hexyl, heptyl, octyl, nonyl and decyl. Representative alkenyl groupsinclude, but are not limited to, vinyl, allyl, butenyl and cyclohexenyl.Representative alkynyl groups include, but are not limited to, ethynyl,1-propynyl, 2-propynyl, 1-butynyl and 2-butynyl. Representativecycloalkyl groups include, but are not limited to, cyclopentyl,cyclohexyl and cyclooctyl substituents. Representative aryl groupsinclude, but are not limited to, phenyl, naphthyl and anthracenyl.Representative aralkyl groups include, but are not limited to, benzyland phenethyl. Representative alkylidenyl groups include methylidenyland ethylidenyl groups. In addition, it should be noted that thehydrocarbyl groups mentioned above can be substituted, that is to sayone of the hydrogen atoms replaced, with linear and branched C₁-C₁₀alkyl, haloalkyl and perhaloalkyl groups, aryl groups and cycloalkylgroups.

Any of R¹ to R⁴ can also be a halohydrocarbyl group, where such groupincludes any of the hydrocarbyls mentioned above where at least one, butless than all, of the hydrogen atoms of the hydrocarbyl are replaced bya halogen (fluorine, chlorine, bromine or iodine). Additionally, any ofR¹ to R⁴ can be a perhalocarbyl, where such group includes any of thehydrocarbyls mentioned above where all of the hydrogen atoms of thehydrocarbyl are replaced by a halogen. Useful perfluorinatedsubstituents include perfluorophenyl, perfluoromethyl, perfluoroethyl,perfluoropropyl, perfluorobutyl and perfluorohexyl.

When the pendant group(s) is an other substituent, any of R¹ to R⁴independently represent linear or branched carboxylic acid, carboxylicacid ester, carboxylic acid ether, ether, alcohol and carbonyl groups.Representative examples of “other” substituents are functionalsubstituents that include, but not limited, to radical selected from—(CR^(†) ₂)_(n)—C(O)OR⁵, —(CR^(†) ₂)_(n)—O—R⁵, —(CR^(†) ₂)_(n)—C(O)—R⁵,—(CR^(†) ₂)_(n)Si—R⁵, —(CR^(†) ₂)_(n)Si(O—R⁵)₃,-A-O—[—(C(R⁵)₂—)_(n)—O—]_(n)—(C(R⁵)₂—)_(n)—OH and R⁵—(Z), where ‘n’independently represents an integer from 0 to 10, R^(†) can be hydrogenor halogen and each R⁵ independently represents hydrogen, halogen, C₁ toC₃₀ alkyl, aryl, aralkyl, alkaryl, alkenyl, alkynyl, cycloalkyl,cycloalkenyl and alkylidenyl groups that can also contain one or morehetero atoms. Further, ‘A’ is a linking group selected from C₁ to C₆linear, branched, or cyclic alkylene, and ‘Z’ is a functional groupselected from hydroxyl, carboxylic acid, amine, thiol, isocyanate andepoxy. Representative hydrocarbyl groups set forth under the definitionof R⁵ are the same as those identified above under the definition of R′to R⁴, above. Further, R⁵ can represent a moiety selected from —C(CH₃)₃,—Si(CH₃)₃, —CH(R³⁷)OCH₂CH₃, —CH(R³⁷)OC(CH₃)₃ or the following cyclicgroups:

-   -   where R³⁷ represents hydrogen or a linear or branched (C₁-C₅)        alkyl group. The alkyl groups include methyl, ethyl, propyl,        i-propyl, butyl, i-butyl, t-butyl, pentyl, t-pentyl and        neopentyl. In the above structures, the single bond line        projecting from the cyclic groups indicates the position where        the cyclic group is bonded to the acid substituent.

Thus, examples of R⁵ include 1-methyl-1-cyclohexyl, isobornyl,2-methyl-2-isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl,tetrahydropyranoyl, 3-oxocyclohexanonyl, mevalonic lactonyl,1-ethoxyethyl and 1-t-butoxy ethyl radicals, as well as thedicyclopropylmethyl (Dcpm), and dimethylcyclopropylmethyl (Dmcp) groupsrepresented by the following structures:

Further, in some embodiments in accordance with the present invention,monomers represented in Structural Formula A above, can have R¹ and R⁴taken together with the two ring carbon atoms to which they are attachedrepresent a substituted or unsubstituted cycloaliphatic group containing4 to 30 ring carbon atoms or a substituted or unsubstituted aryl groupcontaining 6 to 18 ring carbon atoms or combinations thereof. Thecycloaliphatic group can be monocyclic or polycyclic. When unsaturatedthe cyclic group can contain monounsaturation or multiunsaturation, withmonounsaturated cyclic groups being found useful. When substituted, therings contain monosubstitution or multisubstitution wherein thesubstituents are independently selected from hydrogen, linear andbranched C₁-C₅ alkyl, linear and branched C₁-C₅ haloalkyl, linear andbranched C₁-C₅ alkoxy, halogen, or combinations thereof. The radicals R¹and R⁴ can be taken together to form the divalent bridging group,—C(O)-G-(O)C—, which when taken together with the two ring carbon atomsto which they are attached form a pentacyclic ring, where G representsan oxygen atom or the group N(R³⁸), and R³⁸ is selected from hydrogen,halogen, linear and branched C₁-C₁₀ alkyl, and C₆-C₁₈ aryl. Arepresentative structure is shown in below, where m is an integer from 0to 5.

In some embodiments in accordance with Structural Formula A, theperhalohydrocarbyl groups can include perhalogenated phenyl and alkylgroups. In other embodiments, the perfluorinated substituents caninclude perfluorophenyl, perfluoromethyl, perfluoro ethyl,perfluoropropyl, perfluorobutyl and perfluorohexyl. In addition to thehalogen substituents, cycloalkyl, aryl and aralkyl groups of suchembodiments can be further substituted with linear and branched C₁-C₅alkyl and haloalkyl groups, aryl groups and cycloalkyl groups.Non-limiting examples of monomers in accordance with embodiments of thepresent invention include those shown below in Monomer Groups AA, BB,and CC.

In some other embodiments in accordance with Structural Formula A, thepoly(cyclic) olefin monomer includes HFANB, 5-norbornene-2-methanolhydroxylethylether, t-butyl ester of norbornene 5-carboxylic acid,hydroxyethylester of 5-norbornene carboxylic acid, trimethylsilane esterof 5-norbornene carboxylic acid, 5-norbornene-2-methanol acetate,5-norbornene-2-methanol, 5-norbornene-2-ethanol,5-triethoxysilylnorbornene, 1-methylcyclopentyl ester of 5-norbornenecarboxylic acid, tetrahydro-2-oxo-3-furanyl ester of 5-norbornenecarboxylic acid and mixtures thereof.

In some other embodiments in accordance with Structural Formula A, atleast one of R¹ to R⁴ can be a QNHSO₂R⁸ group or aQ^(‡)(CO)O—(CH₂)_(m)—R⁸ group, where Q and Q^(‡) are optional linear orbranched alkyl spacer of 1 to 5 carbons, m is either 0 or an integerfrom 1 to 3 inclusive and R⁸ is a perhalo group of 1 to about 10 carbonatoms.

In some embodiments in accordance Structural Formula A, at least one ofR¹ to R⁴ is one of groups A, B or C:

-   -   where m and Q‡ are as defined above and Q* is a linear or        branched alkyl spacer of 1 to 5 carbons.

In some embodiments encompassing groups A or C, Q^(‡) is not present oris a linear alkyl spacer of 1 to 3 carbons and additionally for group C,Q* is a linear or branched spacer of 3 or 4. In other such embodimentsQ^(‡) is not present or is 1 carbon atom. In other embodimentsencompassing group B, m is either 1 or 2. In exemplary embodiments ofthe encompassing repeating units represented by Structural Formula A, Xis —CH₂—, one of R¹ to R⁴ is group B and the others are each hydrogen, nis 0 and m is 1

In yet other embodiments in accordance with Structural Formula A, atleast one of R¹ to R⁴ is one of groups D, E or F:

-   -   where each X is independently either F or H, each q is        independently an integer from 1 to 3, p is an integer from 1 to        5, Q* is as defined above, and Z is a linear or branched halo or        perhalo spacer of 2 to 10 carbons.

In some embodiments encompassing group D, Q* is one carbon, X is F, q is2 or 3 and p is 2. In some embodiments encompassing group E, Q* is onecarbon and Z is a branched fluorinated alkyl chain of up to 9 carbonsunits. In some embodiments encompassing group F, Q* is one carbon and qis 1 or 2.

In other embodiments in accordance with Structural Formula A, at leastone of R¹ to R⁴ is a group represented by the formula:

-   -   where Q‡ is an optional linear or branched alkyl spacer where if        present is of 1 to 5 carbons. In some other embodiments the        others of R¹ to R⁴ are each hydrogen and Q^(‡) is not present or        is a linear alkyl spacer of 1 to 3 carbons. In still other        embodiments the others of R¹ to R⁴ are each hydrogen and Q^(‡)        is not present or is 1 carbon atom and in yet still other        embodiments, the others of R¹ to R⁴ are each hydrogen and Q‡ is        not present.

In other embodiments in accordance with Structural Formula A, at leastone of R¹ to R⁴ is a group represented by one of H, J or K shown below:

-   -   where Q^(‡) is as defined above and R²⁷ is a linear or branched        alkyl group of 1 to about 5 carbon atoms. It should be noted        that the HJK(acid) group represented above, is derived from one        of the H, J or K groups.

The monomer composition can include any one or multiple variations ofthe poly(cyclic) olefin monomers of Structural Formula A. Otherembodiments in accordance with the present invention encompasshomopolymers and polymers of monomers in accordance with any ofStructural Formula A. In other embodiments, the poly(cyclic) olefinmonomers used to make the polymers of the present invention include oneor more of those shown in FIG. 2 and in Structural Groups AA, BB and CCshown below.

Exemplary polymers of embodiments in accordance with Structural FormulaA include, but are not limited to, the structures depicted in PolymerFormulae A through G in Polymer Group DD represented below:

Embodiments of the invention are directed to any polymers havingrepeating units derived from monomers in accordance with StructuralFormula A. Such repeating units are derived through the polymerizationof such monomers by 2,3 enchainment addition. Thus any repeating unit(A*) is derived from monomer (B*) as shown below:

For embodiments in accordance with the present invention, a palladiumcatalyst complex and a CTAA are added to norbornene-type monomers tocause such monomers to polymerize as described above. Generally, suchembodiments employ single component palladium catalyst complexes such asare described and disclosed in Published U.S. Patent Application Number2005/0187398 A1 in the text of paragraphs [0011] through [0113] and inExamples 1 through 35, which is incorporated herein by reference. Inother embodiments, palladium catalyst complexes such as those describedand disclosed in U.S. Pat. No. 6,455,650 B1 in the text beginning atcolumn 3 line 11 and continuing through column 29 line 45 and pertinentpalladium containing examples, which is incorporated herein byreference, are used.

In the '650 patent, catalyst complex is generally described as:

[(R′)_(z)M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  Catalyst Formula I

-   -   where M represents a Group 10 transition metal such as        palladium; R′ represents an anionic hydrocarbyl ligand; L′        represents a Group 15 neutral electron donor ligand such as a        phosphorus containing ligand; L″ represents a labile neutral        electron donor ligand; x is 1 or 2; y is 0, 1, 2, or 3, wherein        the sum of x, y, and z is 4; and b and d are numbers        representing the number of times the cation complex and weakly        coordinating counter-anion complex (WCA), respectively, are        taken to balance the electronic charge of the overall catalyst        complex.

In the '398 published application, the catalyst complexes are describedas being derived from:

[(E(R)₃)_(a)Pd(Q)(LB)_(b)]_(p)[WCA]_(r)  Catalyst Formula Ia

[(E(R)₃)(E(R)₂R*)Pd(LB)]_(p)[WCA]_(r)  Catalyst Formula Ib

Where in Catalyst Formula Ia, E(R)₃ represents a Group 15 neutralelectron donor ligand where E is selected from a Group 15 element of thePeriodic Table of the Elements, and R independently represents hydrogen(or one of its isotopes), or an anionic hydrocarbyl containing moiety; Qis an anionic ligand selected from a carboxylate, thiocarboxylate, anddithiocarboxylate group; LB is a Lewis base; WCA represents a weaklycoordinating anion; a represents an integer of 1, 2, or, 3; b representsan integer of 0, 1, or 2, where the sum of a+b is 1, 2, or 3; and p andr are integers that represent the number of times the palladium cationand the weakly coordinating anion are taken to balance the electroniccharge on the structure of Catalyst Formula Ia. In an exemplaryembodiment, p and r are independently selected from an integer of 1 and2. And where in Formula Ib, E, R, r, p and E(R)₃ are as defined forCatalyst Formula Ia, and where E(R)₂R* also represents a Group 15neutral electron donor ligand where R* is an anionic hydrocarbylcontaining moiety, bonded to the Pd and having a β hydrogen with respectto the Pd center. In an exemplary embodiment, p and r are independentlyselected from an integer of 1 and 2.

It has also been found that in Catalyst Formula Ia, Q can be selectedfrom acetyl acetonate (“acac”) and its derivatives. Such derivatives canbe thio derivatives where one or more of the acac oxygens are replacedwith a sulfur atom or alkyl derivatives where one or more acac hydrogensare replaced with an appropriate substituent. Where Q is acac or aderivative thereof, a is an integer of 1 or 2; b is an integer of 0 or1, and the sum of a+b is 1 or 2.

As stated herein, a weakly coordinating anion (WCA) is defined as agenerally large and bulky anion capable of delocalization of itsnegative charge, and which is only weakly coordinated to a palladiumcation of the present invention and is sufficiently labile to bedisplaced by solvent, monomer or neutral Lewis base. More specifically,the WCA functions as a stabilizing anion to the palladium cation butdoes not transfer to the cation to form a neutral product. The WCA anionis relatively inert in that it is non-oxidizing, non-reducing, andnon-nucleophilic.

The importance of WCA charge delocalization depends, to some extent, onthe nature of the transition metal comprising the cationic activespecies. It is advantageous that the WCA either does not coordinate tothe transition metal cation, or is one which is only weakly coordinatedto such cation. Further, it is advantageous that the WCA not transfer ananionic substituent or fragment to the cation so as to cause it to forma neutral metal compound and a neutral by-product from such transfer.Therefore, useful WCAs in accordance with embodiments of this inventionare those which are compatible, stabilize the cation in the sense ofbalancing its ionic charge, and yet retain sufficient lability to permitdisplacement by an olefinically unsaturated monomer duringpolymerization. Additionally, such useful WCAs are those of sufficientmolecular size to partially inhibit or help to prevent neutralization ofthe late-transition-metal cation by Lewis bases other than thepolymerizable monomers that may be present in the polymerizationprocess. While not wishing to be bound by any theory, it is believedthat the WCAs in accordance with embodiments of the present inventioncan include anions (listed more to less coordinating), such astrifluoromethanesulfonate (CF₃SO₂ ⁻), tris(trifluoromethyl)methide((CF₃SO₂)₃C), triflimide, BF₄ ⁻, BPh₄ ⁻, PF₆ ⁻, SbF₆ ⁻,tetrakis(pentafluorophenyl)borate (herein abbreviated FABA), andtetrakis[3,5-bis(trifluoromethyl)phenyl]borate ([BAr^(f)]⁻).Furthermore, it is believed the catalytic activity of the proinitiatorsof this invention increases with decreasing coordination of the WCA.Hence, it is believed that in order to obtain a desired catalyticactivity, a WCA and ER₃ should be selected in concert with one another.

As stated herein, a neutral electron donor is defined as any ligandwhich when removed from the palladium metal center in its closed shellelectron configuration, has a neutral charge. Further, an anionichydrocarbyl moiety is defined as any hydrocarbyl group which whenremoved from ‘E’ (see Formulae Ia) in its closed shell electronconfiguration, has a negative charge; and a Lewis base is defined as “abasic substance furnishing a pair of electrons for a chemical bond,”hence it is a donor of electron density.

For such catalysts useful in embodiments in accordance with the presentinvention, E is a Group 15 element of the Periodic Table of the Elementsselected from phosphorus (P), arsenic (As), antimony (Sb), and bismuth(Bi). In Catalyst Formula Ia, the anionic hydrocarbyl containing moietyR is independently selected from, but not limited to, H, linear andbranched (C₁-C₂₀) alkyl, (C₃-C₁₂) cycloalkyl, (C₂-C₁₂) alkenyl, (C₃-C₁₂)cycloalkenyl, (C₅-C₂₀) polycycloalkyl, (C₅-C₂₀) polycycloalkenyl, and(C₆-C₁₂) aryl, and two or more R groups taken together with E can form aheterocyclic or heteropolycyclic ring containing 5 to 24 atoms.Representative heteroatoms include, but are not limited to, oxygen andnitrogen. An exemplary embodiment where two R groups are taken togetherwith E (where E is phosphorus) is eicosyl phobane phosphine (EPN). InFormula Ib, the anionic hydrocarbyl containing moiety R* is selectedfrom, but not limited to, linear and branched (C₂-C₂₀) alkyl, (C₃-C₁₂)cycloalkyl, (C₂-C₁₂) alkenyl, (C₃-C₁₂) cycloalkenyl, (C₅-C₂₀)polycycloalkyl, (C₅-C₂₀) polycycloalkenyl with the proviso that suchanionic hydrocarbyl containing moiety, when bonded to the Pd, will haveat least one 13 hydrogen with respect to the Pd center.

Representative alkyl groups include, but are not limited to, methyl,ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,pentyl and neopentyl. Representative alkenyl groups include, but are notlimited to, vinyl, allyl, iso-propenyl and iso-butenyl. Representativecycloalkyl groups include, but are not limited to, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.Representative polycycloalkyl groups include, but are not limited to,norbornyl and adamantyl. Representative polycycloalkenyl groups include,but are not limited to, norbornenyl and adamantenyl. Representative aryland aralkyl groups include, but are not limited to, phenyl, naphthyl andbenzyl.

Exemplary Group 15 neutral electron donor ligands are, among others,phosphine ligands such as di-t-butylcyclohexylphosphine,dicyclohexyl-t-butylphosphine, tricyclohexylphosphine,tricyclopentylphosphine, dicyclohexyladamantylphosphine,cyclohexyldiadamantylphosphine, triisopropylphosphine,di-tert-butylisopropylphosphine and diisopropyl-tert-butylphosphine.Further it is to be recognized that two phosphine groups can be takentogether to form a diphosphine chelating ligand. Exemplary diphosphinechelating ligands include, but are not limited to,bis(dicyclohexylphosphino)methane; 1,2-bis(dicyclohexylphosphino)ethane;1,3-bis(dicyclohexylphosphino)propane;1,4-bis(dicyclohexylphosphino)butane; and1,5-bis(dicyclohexylphosphino)pentane. Other suitable diphosphineligands are exemplified in the '650 patent previously incorporatedherein.

Lewis bases in accordance with the present invention can be any compoundthat donates an electron pair. The Lewis base can be water or selectedfrom the following type of compounds: alkyl ethers, cyclic ethers,aliphatic or aromatic ketones, primary alcohols, nitriles, cyclic aminesespecially pyridines and pyrazines, and trialkyl or triaryl phosphites.

Exemplary Lewis base ligands include, but are not limited to, water,dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, acetone,benzophenone, acetophenone, methanol, isopropanol, acetonitrile,benzonitrile, tert-butylnitrile, tert-butylisocyanide, xylylisocyanide,pyridine, dimethylaminopyridine, 2,6-dimethylpyridine,4-dimethylaminopyridine, tetramethylpyridine, 4-methylpyridine,pyrazine, tetramethylpyrazine, triisopropylphosphite, triphenylphosphiteand triphenylphosphine oxide. Phosphines can also be included asexemplary Lewis bases so long as they are added to the reaction mediumduring the formation of the single component catalyst of the invention.Examples of Lewis base phosphines include, but are not limited to,triisopropylphosphine, tricyclohexylphosphine, tricyclopentylphosphineand triphenylphosphine.

WCAs in accordance with the present invention are selected from boratesand aluminates, boratobenzene anions, carborane, halocarborane andphosphaborane anions. Representative borate anions include, but are notlimited to, tetrakis(pentafluorophenyl)borate (FABA),tetrakis(3,5-bis(trifluoromethyl)phenyl)borate andtetrakis(2-fluorophenyl)borate. Other useful weakly coordinating anions,for example other borates and aluminates, boratobenzene anions,carborane, halocarborane and phosphaborane anions, can be found in the'398 published application, previously incorporated herein.

Exemplary salts of weakly coordinating anions are N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate (DANFABA) and lithiumtetrakis(pentafluorophenyl)borate 2.5 diethyletherate (LiFABA), amongothers.

Exemplary embodiments in accordance with the present invention utilizeone or more catalysts selected fromtrans-[Pd((OAc)(MeCN(P(i-propyl)₃)₂]FABA,trans-[Pd(OAc)(NCC(CH₃)₃)(P(i-propyl)₃)₂]FABA,trans-[Pd(OAc)(OC(C₆H₅)₂)(P(i-propyl)₃)₂]FABA,trans-[Pd(OAc)(HOCH(CH₃)₂)(P(i-propyl)₃)₂]FABA,trans-[Pd(OAc)(MeCN)(P(cyclohexyl)₃)₂]FABA,trans-[Pd(OAc)(MeCN)(P(cyclohexyl)₂(t-butyl))₂]FABA,[Pd(OAc)(MeCN)(P(octyl)₃)]FABA, [Pd(OAc)(MeCN)(EPN)₂]FABA,[Pd(OAc)(MeCN)(EPN)]FABA, Pd(OAc)₂(P(cyclohexyl)₃)₂FABA,Pd(OAc)₂(P(i-propyl)₃)₂FABA, Pd(OAc)₂(P(i-propyl)₂(phenyl))₂FABA,[Pd(acac)(MeCN)(P(octyl)₃)]FABA, [Pd(acac)(MeCN)(P(i-propyl)₃)]FABA,[Pd(acac)(MeCN)(EPN)]FABA, [Pd(acac)(NCC(CH₃)₃)(P(i-propyl)₃)]FABA,trans-[Pd(acac)(OC(C₆H₅)₂)(P(1-propyl)₃)]FABA,trans-[Pd(acac)(HOCH(CH₃)₂)(P(i-propyl)₃)]FABA, andtrans-[Pd(acac)(MeCN)(P(cyclohexyl)₃)]FABA.

For embodiments in accordance with the present invention, anon-phosphorus containing, or phosphorous-free, palladium catalystcomplex and a CTAA are added to norbornene-type monomers to cause suchmonomers to polymerize by 2,3-enchainment addition. In some suchembodiments, the non-phosphorus containing palladium catalyst employedis depicted by Formula II:

-   -   where A is a bidentate monoanionic ligand represented by        Catalyst Formula III, below:

-   -   and where each of X and Y are independently selected from O, N,        or S and where R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶        independently represent hydrogen, methyl, linear or branched        C₂-C₁₀ alkyl, C₃-C₁₀ cycloalkyl, C₇-C₂₀ aralkyl, or C₆-C₂₄ aryl        or substituted aryl, n represents an integer of 0, 1, or 2; and        when either X or Y are O or S, R¹⁰ and R¹⁴, respectively, do not        exist.

Further, R¹¹ and R¹² and the carbons to which they are attached, or R¹³and the carbon to which it is attached and R¹⁴ and X can form asubstituted or unsubstituted aromatic ring.

In some representations of Catalyst Formula III the bidentatemonoanionic ligand (X—Y) is a chelate characterized by the presence ofbonds from two bonding sites within the same ligand to a central metalatom. In other representations the bidentate monoanionic ligand is ahemilabile group or ligand, that is to say a chelate characterized bythe presence of bonds from two bonding sites within the same ligand to acentral metal atom, where one of the bonds is readily broken by asolvent to render a metal center bound to one terminus of the anionicgroup and thereby generating a vacant coordination site at the metalcenter.

In Catalyst Formula III, the bidentate anionic species is believed to begenerated from the neutral species HX—Y. The groups X and Y are selectedfrom O, N, or S, where R¹⁰, R¹¹, R¹², R¹³ and R¹⁴, as shown in X—Y(a)and X—Y(b), are as defined above. Exemplary X—Y ligands are β-diketonato(O—O), β-diketiminato (N—N), β-ketiminato (N—O) and Schiff base (N—O)ligands. Thus such bidentate anionic species are believed to exist intautomeric forms as shown below:

In other embodiments of the present invention, the bidentate anion X—Yis selected from:

In still other embodiments the bidentate anion X—Y is one of thetropolone derivatives shown below or a derivative of any otherappropriate substituted or unsubstituted hydrocarbyl.

In some embodiments of the present invention, the palladium source andX—Y sources are selected from Pd(acac)₂,bis(trifluoroacetylacetonate)Pd, bis(hexafluoroacetylacetonate)Pd;bis(dibenzoylmethanate)Pd, bis(benzoylacetonate)Pd,bis(tetramethylheptanedionate)Pd, or bis(tropolonato)palladium (II).

Some other embodiments in accordance with the present inventionencompass non-phosphorus containing palladium catalysts represented byCatalyst Formula IV, shown below:

-   -   where L is nitrogen, oxygen, sulfur, an alkene, or chlorinated        alkane containing neutral labile donor ligands and WCA is a        weakly coordinating anion; and where R²⁰, R²¹ and R²² each        independently represent a hydrogen, a halogen, a linear or        branched C₁ to C₅ alkyl, a C₅ to C₁₀ cycloalkyl, a linear or        branched C₁ to C₅ alkenyl, C₆ to C₃₀ aryl, C₇ to C₃₀ aralkyl,        where each of the above can be optionally substituted with a        substituent selected from a linear or branched C₁ to C₅ alkyl, a        linear or branched C₁ to C₅ haloalkyl, one or more halogens and        a phenyl which can be optionally substituted with a linear or        branched C₁ to C₅ alkyl, a linear or branched C₁ to C₅        haloalkyl, and one or more halogens. Further any two of R²⁰, R²¹        and R²² can be linked together with the carbon atoms to which        they are attached to form a cyclic or multicyclic ring which can        be optionally substituted with a linear or branched C₁ to C₅        alkyl, a linear or branched C₁ to C₅ haloalkyl, and one or more        halogens. Exemplary allylic ligands that are encompassed by the        cationic complexes of the present invention include, but are not        limited to, allyl, 2-chloroallyl, crotyl, 1,1-dimethyl allyl,        2-methylallyl, 1-phenylallyl, 2-phenylallyl and β-pinenyl.

Additional examples of allyl ligands are found in R. G. Guy and B. L.Shaw, Advances in Inorganic Chemistry and Radiochemistry, Vol. 4,Academic Press Inc., New York, 1962; J. Birmingham, E. de Boer, M. L. H.Green, R. B. King, R. Koster, P. L. I. Nagy, G. N. Schrauzer, Advancesin Organometallic Chemistry, Vol. 2, Academic Press Inc., New York,1964; W. T. Dent, R. Long and A. J. Wilkinson, J. Chem. Soc., (1964)1585; and H. C. Volger, Rec. Tray. Chim. Pay Bas, 88 (1969) 225.

Representative labile neutral electron donor ligands (L) include, butare not limited to, reaction diluents, reaction monomers, DMF, DMSO,dienes including C₄ to C₁₀ aliphatic and C₄ to C₁₀ cycloaliphatic dienesrepresentative dienes include butadiene, 1,6-hexadiene, andcyclooctadiene (COD), water, chlorinated alkanes, alcohols, ethers,ketones, nitriles, arenes, organic carbonates and esters. Representativechlorinated alkanes include but are not limited to dichloromethane,1,2-dichloroethane, and carbon tetrachloride.

Suitable alcohol ligands can be selected from alcohols of the formulaR¹⁷OH, where R¹⁷ represents a linear and branched C₁ to C₂₀ alkyl, alinear and branched C₁ to C₂₀ haloalkyl, a substituted and unsubstitutedC₃ to C₂₀ cycloalkyl, a substituted and unsubstituted C₆ to C₁₈ aryl,and a substituted and unsubstituted C₆ to C₁₈ aralkyl. When substituted,the cycloalkyl, aryl and aralkyl groups can be monosubstituted ormultisubstituted, where the substituents are independently selected fromhydrogen, linear and branched C₁ to C₁₂ alkyl, linear and branched C₁ toC₅ haloalkyl, linear and branched C₁ to C₅ alkoxy, C₆ to C₁₂ aryl, andhalogen selected from chlorine, bromine, and fluorine. Representativealcohols include, but are not limited to, methanol, ethanol, n-propanol,isopropanol, butanol, hexanol, t-butanol, neopentanol, phenol,2,6-di-1-propylphenol, 4-t-octylphenol, 5-norbornene-2-methanol, anddodecanol.

Suitable ether ligands and thioether ligands can be selected from ethersand thioethers of the formulae (R¹⁸—O—R¹⁸) and (R¹⁸—S—R¹⁸),respectively, where R¹⁸ independently represents linear and branched C₁to C₁₀ alkyl radicals, linear and branched C₁ to C₂₀ haloalkyl radicals,substituted and unsubstituted C₃ to C₂₀ cycloalkyl radicals, linear andbranched C₁ to C_(u) alkoxy radicals, substituted and unsubstituted C₆to C₁₈ aryl radicals, and substituted and unsubstituted C₆ to C_(is)aralkyl radicals. When substituted, the cycloalkyl, aryl and aralkylgroups can be monosubstituted or multisubstituted, where suchsubstituents are independently selected from hydrogen, and radicals suchas linear and branched C₁ to C₁₂ alkyl, linear and branched C₁ to C₅haloalkyl, linear and branched C₁ to C₅ alkoxy, and C₆ to C₁₂ aryl.Further, such substituents can be a halogen selected from chlorine,bromine, and fluorine. Still further, each R¹⁸ can be taken togetherwith the oxygen or sulfur atom to which they are attached to form acyclic ether or cyclic thioether, respectively. Representative ethersand thioethers include, but are not limited to, dimethyl ether, dibutylether, methyl-t-butyl ether, di-1-propyl ether, diethyl ether, dioctylether, 1,4-dimethoxyethane, THF, 1,4-dioxane and tetrahydrothiophene.

The nitrile ligands can be represented by the formula R^(12′)CN, whereR^(12′) represents hydrogen, linear and branched C₁ to C₂₀ alkyl, linearand branched C₁ to C₂₀ haloalkyl, substituted and unsubstituted C₃ toC₂₀ cycloalkyl, substituted and unsubstituted C₆ to C₁₈ aryl, andsubstituted and unsubstituted C₆ to C₁₈ aralkyl. When substituted, thecycloalkyl, aryl and aralkyl groups can be monosubstituted ormultisubstituted, where the substituents are independently selected fromhydrogen, linear and branched C₁ to C₁₂ alkyl, linear and branched C₁ toC₅ haloalkyl, linear and branched C₁ to C₅ alkoxy, C₆ to C₁₂ aryl, andhalogen selected from chlorine, bromine, and fluorine. Representativenitriles include but are not limited to acetonitrile, propionitrile,benzonitrile, benzyl cyanide, and 5-norbornene-2-carbonitrile.

The arene ligands can be selected from substituted and unsubstituted C₆to C₁₂ arenes containing monosubstitution or multisubstitution, wherethe substituents are independently selected from hydrogen, linear andbranched C₁ to C₁₂ alkyl, linear and branched C₁ to C₅ haloalkyl, linearand branched C₁ to C₅ alkoxy, C₆ to C₁₂ aryl, and halogen selected fromchlorine, bromine, and fluorine. Representative arenes include but arenot limited to toluene, benzene, o-, m-, and p-xylenes, mesitylene,fluorobenzene, o-difluorobenzene, p-difluorobenzene, chlorobenzene,pentafluorobenzene, o-dichlorobenzene, and hexafluorobenzene.

Representative carbonates include but are not limited to ethylenecarbonate and propylene carbonate.

Representative esters include but are not limited to ethyl acetate andi-amyl acetate.

The weakly coordinating counteranion complex, [WCA], of Formula IV canbe selected from borates and aluminates, boratobenzene anions, carboraneand halocarborane anions.

The borate and aluminate weakly coordinating counteranions arerepresented by WCA Formulae V and VI below:

[M′(R²⁴′)(R^(25′))(R^(26′))(R^(27′))]⁻  V

[M′(OR^(28′))(OR^(29′))(OR^(30′))(OR^(31′))]⁻  VI

-   -   where in WCA Formula V M′ is boron or aluminum and R^(24′),        R^(25′), R^(26′), and R^(27′) independently represent fluorine,        linear and branched C₁ to C₁₀ alkyl, linear and branched C₁ to        C₁₀ alkoxy, linear and branched C₃ to C₅ haloalkenyl, linear and        branched C₃ to C₁₂ trialkylsiloxy, C₁₈ to C₃₆ triarylsiloxy,        substituted and unsubstituted C₆ to C₃₀ aryl, and substituted        and unsubstituted C₆ to C₃₀ aryloxy groups where R^(24′) to        R^(27′) can not all simultaneously represent alkoxy or aryloxy        groups. When substituted the aryl groups can be monosubstituted        or multisubstituted, where the substituents are independently        selected from linear and branched C₁ to C₅ alkyl; linear and        branched C₁ to C₅ haloalkyl, linear and branched C₁ to C₅        alkoxy, linear and branched C₁ to C₅ haloalkoxy, linear and        branched C₁ to C₁₂ trialkylsilyl, C₆ to C₁₈ triarylsilyl, and        halogen selected from chlorine, bromine, and fluorine.        Representative borate anions under WCA Formula V include but are        not limited to tetrakis(pentafluorophenyl)borate,        tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,        tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate,        tetrakis(4-fluorophenyl)borate,        tetrakis(3,5-difluorophenyl)borate,        tetrakis(2,3,4,5-tetrafluorophenyl)borate,        tetrakis(3,4,5,6-tetrafluorophenyl)borate,        tetrakis(3,4,5-trifluorophenyl)borate,        methyltris(perfluorophenyl)borate,        ethyltris(perfluorophenyl)borate,        phenyltris(perfluorophenyl)borate,        tetrakis(1,2,2-trifluoroethylenyl)borate,        tetrakis(4-tri-i-propylsilyltetrafluorophenyl)borate,        tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate,        (triphenylsiloxy)tris(pentafluorophenyl)borate,        (octyloxy)tris(pentafluorophenyl)borate,        tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,        tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,        and        tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate.

Representative aluminate anions under Formula WCA V include but are notlimited to tetrakis(pentafluorophenyl) aluminate,tris(perfluorobiphenyl) fluoroaluminate,(octyloxy)tris(pentafluorophenyl) aluminate,tetrakis(3,5-bis(trifluoromethyl)phenyl) aluminate, andmethyltris(pentafluorophenyl) aluminate.

In WCA Formula VI, above, M′ is boron or aluminum, R^(28′), R^(29′),R^(30′), and R^(31′) independently represent linear and branched C₁ toC₁₀ alkyl, linear and branched C₁ to C₁₀ haloalkyl, C₂ to C₁₀haloalkenyl, substituted and unsubstituted C₆ to C₃₀ aryl, andsubstituted and unsubstituted C₇ to C₃₀ aralkyl groups, subject to theproviso that at least three of R^(28′) to R^(31′) must contain a halogencontaining substituent. When Substituted the aryl and aralkyl groups canbe monosubstituted or multisubstituted, where the substituents areindependently selected from linear and branched C₁ to C₅ alkyl, linearand branched C₁ to C₅ haloalkyl, linear and branched C₁ to C₅ alkoxy,linear and branched C₁ to C₁₀ haloalkoxy, and halogen selected fromchlorine, bromine, and fluorine. The groups OR^(28′) and OR^(29′) can betaken together to form a chelating substituent represented by—O—R^(32′)—O—, where the oxygen atoms are bonded to M′ and R^(32′) is adivalent radical selected from substituted and unsubstituted C₆ to C₃₀aryl and substituted and unsubstituted C₇ to C₃₀ aralkyl. Generally, theoxygen atoms are bonded, either directly or through an alkyl group, tothe aromatic ring in the ortho or meta position. When substituted thearyl and aralkyl groups can be monosubstituted or multisubstituted,where the substituents are independently selected from linear andbranched C₁ to C₅ alkyl, linear and branched C₁ to C₅ haloalkyl, linearand branched C₁ to C₅ alkoxy, linear and branched C₁ to C₁₀ haloalkoxy,and halogen selected from chlorine, bromine, and fluorine.Representative structures of divalent R^(32′) radicals are illustratedbelow:

-   -   where R^(33′) independently represents hydrogen, linear and        branched C₁ to C₅ alkyl, linear and branched C₁ to C₅ haloalkyl,        and halogen selected from chlorine, bromine, and fluorine;        R^(34′) can be a monosubstituent or taken up to four times about        each aromatic ring depending on the available valence on each        ring carbon atom and independently represents hydrogen, linear        and branched C₁ to C₅ alkyl, linear and branched C₁ to C₅        haloalkyl, linear and branched C₁ to C₅ alkoxy, linear and        branched C₁ to C₁₀ haloalkoxy, and halogen selected from        chlorine, bromine, and fluorine; and n″ independently represents        an integer from 0 to 6. It should be recognized that when n″ is        0 the oxygen atom in the formula —O—R^(32′)—O— is bonded        directly to a carbon atom in the aromatic ring represented by        R^(32′). In the above divalent structural formulae the oxygen        atom(s), i.e., when n″ is 0, and the methylene or substituted        methylene group(s), —(C(R^(33′))₂)_(n″)—, are generally located        on the aromatic ring in the ortho or meta positions.        Representative chelating groups of the formula —O—R^(32′)—O—        include but are not limited to are        2,3,4,5-tetrafluorobenzenediolate (—OC₆F₄O—),        2,3,4,5-tetrachlorobenzenediolate (—OC₆Cl₄O—),        2,3,4,5-tetrabromobenzenediolate (—OC₆Br₄O—), and        bis(1,1′-bitetrafluorophenyl-2,2′-diolate).

Representative borate and aluminate anions represented by WCA Formula VIinclude but are not limited to [B(OC(CF₃)₃)₄]—, [B(OC(CF₃)₂CH₃)₄]—,[B(OC(CF₃)₂H)₄]—, [B(OC(CF₃)(CH₃)H)₄]—, [Al(OC(CF₃)₂Ph)₄]—,[B(OCH₂(CF₃)₂)₄]—, [Al(OC(CF₃)₂C₆H₄CH₃)₄]—, [Al(OC(CF₃)₃)₄]—,[Al(OC(CF₃)(CH₃)H)₄]—, [Al(OC(CF₃)₂H)₄]—, [Al(OC(CF₃)₂C₆H₄-4-i-Pr)₄]—,[Al(OC(CF₃)₂C₆H₄-4-t-butyl)₄]—, [Al(OC(CF₃)₂C₆H₄-4-SiMe₃)₄]—,[Al(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄]—,[Al(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-si-i-Pr₃)₄]—,[Al(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄]—, [Al(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄]—, and[Al(OC(CF₃)₂C₆F₅)₄]—.

Boratobenzene anions useful as the weakly coordinating counteranion arerepresented by WCA Formula VII below:

-   -   where R^(34′) is selected from fluorine, fluorinated        hydrocarbyl, perfluorocarbyl, and fluorinated and perfluorinated        ethers. As used here and throughout the specification, the term        halohydrocarbyl means that at least one hydrogen atom on the        hydrocarbyl radical, e.g., alkyl, alkenyl, alkynyl, cycloalkyl,        aryl, and aralkyl groups, is replaced with a halogen atom        selected from chlorine, bromine, iodine, and fluorine (e.g.,        haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, haloaryl,        and haloaralkyl). The term fluorohydrocarbyl means that at least        one hydrogen atom on the hydrocarbyl radical is replaced by        fluorine. The degree of halogenation can range from at least one        hydrogen atom being replaced by a halogen atom (e.g., a        monofluoromethyl group) to full halogenation (perhalogenation)        where all hydrogen atoms on the hydrocarbyl group have been        replaced by a halogen atom (e.g., perhalocarbyl such as        trifluoromethyl(perfluoromethyl)). Some of the fluorinated        hydrocarbyl and perfluorocarbyl radicals employed in embodiments        in accordance with the present invention contain 1 to 24 carbon        atoms, others 1 to 12 carbon atoms and still others 6 carbon        atoms and can be linear or branched, cyclic, or aromatic. The        fluorinated hydrocarbyl and perfluorocarbyl radicals include but        are not limited to fluorinated and perfluorinated linear and        branched C₁ to C₂₄ alkyl, fluorinated and perfluorinated C₃ to        C₂₄ cycloalkyl, fluorinated and perfluorinated C₂ to C₂₄        alkenyl, fluorinated and perfluorinated C₃ to C₂₄ cycloalkenyl,        fluorinated and perfluorinated C₆ to C₂₄ aryl, and fluorinated        and perfluorinated C₇ to C₂₄ aralkyl. The fluorinated and        perfluorocarbyl ether substituents are represented by the        formulae —(CH₂)_(m)OR^(36′), or —(CF₂)_(m)OR^(36′) respectively,        where R^(36′) is a fluorinated or perfluorocarbyl group as        defined above, m is an integer of 0 to 5. It is to be noted that        when m is 0 the oxygen atom in the ether moiety is directly        bonded attached to the boron atom in the boratobenzene ring.

Advantageous R^(34′) radicals include those that are electronwithdrawing in nature such as, for example, fluorinated andperfluorinated hydrocarbyl radicals selected from trifluoromethyl,perfluoroethyl, perfluoropropyl, perfluoroisopropyl, pentafluorophenyland bis(3,5-trifluoromethyl)phenyl.

R^(35′) independently represents hydrogen, halogen, perfluorocarbyl, andsilylperfluorocarbyl radicals, where the perfluorocarbyl andsilylperfluorocarbyl are as defined previously. While the halogen groupscan be any appropriate halogen, generally chlorine or fluorine areselected. When R^(35′) is halogen, perfluorocarbyl, and/orsilylperfluorocarbyl, the radical(s) are generally ortho or para to theboron atom in the boratobenzene ring.

Additional representative boratobenzene anions include but are notlimited to [1,4-dihydro-4-methyl-1-(pentafluorophenyl)]-2-borate,4-(1,1-dimethyl)-1,2-dihydro-1-(pentafluorophenyl)-2-borate,1-fluoro-1,2-dihydro-4-(pentafluorophenyl)-2-borate, and1-[3,5-bis(trifluoromethyl)phenyl]-1,2-dihydro-4-(pentafluorophenyl)-2-borate.

Carborane and halocarborane anions useful as the weakly coordinatingcounteranion include but are not limited to CB₁₁(CH₃)₁₂—, CB₁₁H₁₂—,1-C₂H₅CB₁₁H₁₁—, 1-Ph₃SiCB₁₁H₁₁—, 1-CF₃CB₁₁H₁₁—, 12-BrCB₁₁H₁₁—,12-BrCB₁₁H₁₁—, 7,12-Br₂CB₁₁H₁₀—, 12-ClCB₁₁H₁₁—, 7,12-Cl₂CB₁₁H₁₀—,1-H—CB₁₁F₁₁—, 1-CH₃—CB₁₁F₁₁F—, 1-CF₃—CB₁₁F₁₁—, 12-CB₁₁H₁₁F—,7,12-CB₁₁H₁₁F₁₂—, 7,9,12-CB₁₁H₁₁F₃—, CB₁₁H₆Br₆—, 6-CB₉H₉F—,6,8-CB₉H₈F₂—, 6,7,8-CB₉H₇F₃—, 6,7,8,9-CB₉H₆F₄—, 2,6,7,8,9-CB₉H₅F₅—,CB₉H₅Br₅—, CB₁₁H₆Cl₆—, CB₁₁H₆F₆—, CB₁₁H₆F₆—, CB₁₁H₆I₆—, CB₁₁H₆Br₆—,6,7,9,10,11,12-CB₁₁H₆F₆—, 2,6,7,8,9,10-CB₉H₅F₅—, 1-H—CB₉F₉—,12-CB₁₁H₁₁(C₆H₅)—, 1-C₆F₅—CB₁₁H₅Br₆—, CB₁₁Me₁₂-, CB₁₁(CF₃)₁₂—,Co(B₉C₂H₁₁)₂—, CB₁₁(CH₃)₁₂—, CB₁₁(C₄H₉)₁₂—, CB₁₁(C₆H₁₃)₁₂—,Co(C₂B₉H₁₁)₂—, Co(Br₃C₂B₉H₈)₂— and dodecahydro-1-carbadodecaborate.

Still other useful anions can also be selected from highly fluorinatedand perfluorinated alkylsuflonyl and arylsulfonyl containing anionsrepresented by the formulae (R⁴⁰SO₂)₂CH—, (R⁴⁰SO₂)₃C— and (R⁴⁰SO₂)₂N—,where R⁴⁰ independently represents a linear and branched C₁ to C₂₀highly fluorinated or perfluorinated alkyl, a C₅ to C₁₅ highlyfluorinated or perfluorinated cycloalkyl and a C₆ to C₂₂ highlyfluorinated or perfluorinated aryl. Optionally, the above alkyl andcycloalkyl groups can contain one or more heteroatoms such as divalentoxygen, trivalent nitrogen and hexavalent sulfur. Further, any two ofR⁴⁰ can be taken together within a cyclic structure. Still further,generally, the aforementioned highly fluorinated groups have at leasthalf of the hydrogens replaced with fluorines and typically at least 2of every 3, and in some embodiments, 3 of every 4 hydrogens are replacedwith fluorines. In some highly fluorinated embodiments, some or all ofthe remaining hydrogens are replaced with either bromines or chlorines.

Some representative highly fluorinated and perfluorinated alkylsulfonyland arylsulfonyl containing groups are disclosed in U.S. Pat. No.6,455,650, entitled “Catalyst and Methods for PolymerizingCyclicolefins”, to Lipian et al., at column 25, lines 17 to 49,inclusive, which is incorporated herein by reference.

Advantageous exemplary salts of weakly coordinating anions areN,N-dimethylanilinium tetrakis(pentafluorophenyl)_(b) orate (DANFABA)and lithium tetrakis(pentafluorophenyl)borate 2.5 diethyletherate(LiFABA), and N,N-dimethylanilinium tris((trifluoromethyl)sulfonyl)methide among others.

Exemplary embodiments in accordance with the present invention utilizeone or more non-phosphorus containing catalysts selected frompalladium(II) acetate-[Pd(OAc)₂], palladium(II)acetylacetonate-[Pd(acac)₂], palladium(II)hexafluoroacetylacetonate—[Pd(CF₃COCHCOCF₃)₂], palladium(II)bis(tetramethylheptanedionato), palladium(II) bis(benzoylacetonato),(allyl)palladium(II) bis(acetonitrile)tris((trifluoromethyl)sulfonyl)methide, (allyl)palladium(II)bis(acetonitrile)tetrakis(pentafluorophenyl)borate, (acac)palladium(II)bis(acetonitrile)tetrakis(pentafluorophenyl)borate and(t-buacac)palladium(II)di(t-butylamine)tetrakis(pentafluorophenyl)borate.

In some embodiments in accordance with the present invention, the CTAAis an acid such as formic acid, thio-formic acid or another suchcompound. An exemplary embodiment of the CTAA is formic acid.

In some embodiments of the present invention, a mixture including amonomer composition, the CTAA and a palladium catalyst is exposed to atemperature at which the above-described catalysts can effectpolymerization of the monomers. In some embodiments the temperature isfrom an ambient temperature to 250° C. For some exemplary embodiments,the aforementioned mixture is heated to a temperature of at least 30°C., in some cases of at least 70° C. and, in other cases, at least 150°C.

The following examples are provided for illustrative purposes only andare not intended to limit the invention in any way. The ratios ofmonomers recited in the title of such experiments represent the molarfeed ratio of such monomers in the reaction mixture and is generallyfound to be representative of the final composition of repeating unitsin the polymer. Further, for each experiment a general procedure forforming the specific polymer is provided followed by a tablerepresenting the results of two or more repetitions of such procedurewhere the mole percent of the CTAA was varied to demonstrate the effectof such a change on the molecular weight and/or conversion rate of theresultant polymer. In all cases this mole percent is based on the amountof monomer present in the particular experimental description and ispresented in the accompanying tables as “% Formic Acid”. In someexperiments more than one table is shown to illustrate the effect of thevarying amounts CTAA for the polymerization of specific monomers withalternate catalysts. However, to facilitate the comparison of thevarious results presented hereinbelow, formic acid was employed as theCTAA for each of the experiments presented.

In the presentation of such experimental data, abbreviations are used tosimplify the naming of monomers and catalysts. The following listing ofthose abbreviations provides an appropriate name for each of suchabbreviations:

Monomers

HFANB 5-(2-hydroxy-2,2-bistrifluoromethyl)ethyl-2-norbornene TFSNBN-(bicyclo [2.2.1]hept-5-en-2-ylmethyl)-1,1,1-trifluoromethanesulfonamide FPCNB pentafluoroester of5-norbornene-2-carboxylic acid MeOAcNB 2-hydroxymethyl-5-norborneneacetate PhOAcNB 2-(4-phenyl acetate)-5-norbornene t-BuEsNB t-butylesterof 5-norbornene-2-caboxylic acid MCPNB 1-methylcyclopentyl-5-norborneneNB norbornene; TFENB bicyclo[2.2.1]hept-5-ene-2-carboxylic acidtetrahydro-2-oxo-3-furanyl ester; TESNB 2-triethoxylsilyl-5-norbornene;AGENB 2-methyl glycidyl ther-5-norbornene; Acid NBbicyclo[2.2.1]hept-5-ene-2-carboxylic acid; DecNB 5-decyl-2-norbornene;PENB 5-Phenylethyl-2-norbornene; BuNB 5-butyl-2-norbornene; NBC₂H₄CO₂Etethyl-5-norbornenepropionate;

Co-Catalysts and Catalysts

DANFABA dimethylanilinium tetrakis (pentafluorophenyl) borate LiFABA Litetrakis(pentafluorophenyl)borate etherate Pd-641 (allyl)palladium(II)bis(acetonitrile)tris((trifluoromethyl)sulfonyl)methide; Pd-910(allyl)palladium(II) bis(acetonitrile)tetrakis(pentafluorophenyl)borate;Pd-304 palladium(II) acetylacetonate; Pd-444tetra(acetonitrile)palladium(II)tetrafluoroborate₂; Pd-916 Pd₂(dba)₃Pd-917 [(1,4-benzoquinone)(norbornene)palladium(0)] dimer Pd-967(acac)palladium(II)bis(acetonitrile)tetrakis(pentafluorophenyl)borate]Pd-1115 (t-buacac)palladium(II) di(t-butylamine)tetrakis(pentafluorophenyl)borate]. Pd-1206(acetonitrile)bis(triisopropylphosphine)palladium(acetate) FABA Pd-1394(acetonitrile)bis(t-butyldicyclohexylphosphine)palladium(acetate) FABAPd-1627 (acetonitrile)bis(tri-octylphosphine)palladium(acetate) FABAPd-1731 (acetonitrile)bis(eicosyl phobane phosphine)palladium(acetate)FABA Pd-1296(acetonitrile)(tri-octylphosphine)palladium(acetylacetonate) FABAPd-1348 (acetonitrile)(eicosyl phobanephosphine)palladium(acetylacetonate) FABA

EXAMPLES

Examples 1-12 are illustrative of polymerizations that employ aphosphorus containing catalyst in accordance with Formulae Ia or Ib. Inexamples 1 and 2 the activation effect of a CTAA such as formic acid isdemonstrated. That is to say that such examples show that by increasingthe amount of such a CTAA, the percent conversion of the monomers,charged to the reaction vessel, into a polymer increases. Examples 10-12are illustrative of the effect that a CTAA such as formic acid has onboth the molecular weight Mw of the resultant polymer and the percentconversion. Examples 3-8 are illustrative of the effect that formic acidhas on the molecular weight (Mw) of polymers that are obtained from thepolymerization of various norbornene-type polymers using phosphoruscontaining catalyst when conversions are at or near 100 percent.

Catalyst Examples 1-7 are illustrative of methods of formingnon-phosphorus containing catalysts that are in accordance with CatalystFormulae II or III; and Examples 13-42 are illustrative ofpolymerizations that employ such non-phosphorus containing catalysts.Comparative Examples 1 and 2 demonstrate that a CTAA such as formic acidhas essentially no effect in controlling the molecular weight ofpolymers made using the non-phosphorous containing catalysttetra(acetonitrile)palladium(II)tetrafluoroborate₂ (Pd-444).

Common to all examples is that the reagents used are essentially oxygenfree. That is to say that, either the reagents and solvents mentionedare charged into a reaction vessel and then sparged with nitrogen for aperiod of time believed sufficient to remove essentially all dissolvedoxygen, or such reagents and solvents are individually sparged prior totheir use and stored under a nitrogen blanket until they are charged tothe reaction vessel. Therefore it will be understood that while aspecific experimental description will not refer to either of the abovemethods of providing oxygen free reagents and solvents, one or the otherwas employed. Further, while not specifically mentioned in any specificexample, an appropriate method of stirring or otherwise agitating thecontents of a reaction vessel was provided.

In addition, molecular weight (Mw) was determined by gel permeationchromatography (GPC) using poly(styrene) standards. The percent (%)conversion of the monomers to polymer was determined gravimetricallyusing a total solids analyzer (Mettler Toledo HR73 halogen moistureanalyzer) or by using well known GPC methods.

The optical density (OD) of the Polymers, where provided, was determinedby the following method: (1) a 20 weight percent solution of the desiredpolymer was formed using propylene glycol methyl ether acetate (PGMEA);(2) the solution was dispensed onto a 1-inch quartz wafer and spun at500 rpm for 15 sec and then 2000 rpm for 60 sec; (3) after the waferswere baked for 120 sec at 130° C., the optical absorbance was measuredat 193 nm using a Cary 400 Scan UV-Vis spectrophotometer; (4) thethickness of the films was measured using a TENCOR Profilometer afterthe films were scored and the optical density (OD) of the filmcalculated by dividing the absorbance by the thickness (in microns).

Samples for MALDI-TOF MS were prepared in the following manner: (1) THFsolutions of a polymer sample (0.1 mg/mL) and dithranol(1,8,9-anthracenetriol, 0.2 mg/mL) were prepared; (2) sodiumtrifluoroacetate was dissolved in methanol (0.3 mg/mL), and 30 μL ofsuch solution was added to 1 mL of the polymer sample solution; (3)equal volumes (30 μL each) of the sample/sodium trifluoroacetate anddithranol solutions were mixed together; and (4) 1 μL of such mixturedeposited via syringe onto a stainless steel MALDI plate and allowed todry. The instrument used was a Bruker Reflex III MALDI-TOF-MS, operatedin either linear or reflectron mode with delayed ion extraction.

Example 1 Polymerization of TFSNB/FPCNB (75/25)

An appropriate sized reaction vessel was charged with TFSNB, 77.0 g (302mmol), FPCNB, 27.0 g (100 mmol), 116.5 g toluene and 38.8 g ethylacetate. The vessel was sealed and transferred to a dry box. Pd-1206(0.035 g, 0.027 mmol) and DANFABA (0.066 g, 0.082 mmol) were added tothe reaction vessel, the contents mixed and 40.0 g portions of thissolution was transferred to a second appropriate size vessel, sealed andtaken out of the dry box. The desired amount of formic acid was addedand the solution was heated to 100° C. and stirred for 17 hours. Thereaction mixture was then allowed to cool to room temperature andanalysis (for molecular weight and conversion) were performed.

TABLE 1 Example % Formic Acid Conversion Mw Mw/Mn 1a 0% 34.4% 93478 2.481b 2% 86.6% 11009 1.81 1c 4% 90.2% 7571 1.72

Example 2 Polymerization of MCPNB/TFENB/TFSNB (40/30/30)

An appropriate sized reaction vessel was charged with 4.40 g (20.0 mmol)MCPNB, 3.36 g (15.0 mmol) TFENB, 3.83 g (15.0 mmol) TFSNB, 12.9 gtoluene, 4.32 g ethyl acetate and a stir bar. This solution was sealedand transferred to a dry box. LIFABA (0.065 g (0.075 mmol)) and Pd-1394(0.035 g (0.025 mmol)) were added, sealed and the vessel was taken outof the dry box. The desired amount of formic acid was added and thesolution was heated to 90° C. and stirred for 17 hours. The reactionmixture was then allowed to cool to room temperature and analysis (formolecular weight and conversion) were performed.

TABLE 2 Example % Formic Acid Conversion MW Mw/Mn 2a 0% 47% 65169 2.722b 4% 54% 6710 3.03 2c 8% 90% 3523 2.16 2d 12%  82% 2224 1.69

Example 3 Polymerization of HFANB/t-BuEsNB (80/20)

An appropriate sized reaction vessel was charged with 10.9 g (40.0 mmol)HFANB, 1.94 g (10.0 mmol) t-BuEsNB, 14.4 g toluene, 4.81 g ethyl acetateand stirred. This solution was sealed and transferred to a dry box.DANFABA (0.060 g (0.075 mmol)) and Pd-1206 (0.030 g (0.025 mmol)) wereadded, sealed and the vessel was taken out of the dry box. The desiredamount of formic acid was added and the solution was heated to 100° C.and stirred for 16 hours. The reaction mixture was then allowed to coolto room temperature and analysis (for molecular weight and conversion)were performed.

TABLE 3 Example % Formic Acid Conversion MW Mw/Mn 3a  0% 97% 94196 2.863b  8% 99% 7683 1.97 3c 12% 99% 5063 1.86 3d 16% 99% 6033 1.91

Example 4 Polymerization of TFSNB/FPCNB (80/20)

An appropriate sized reaction vessel was charged with 8.16 g (32.0 mmol)TFSNB, 2.16 g (8.00 mmol) FPCNB, 12.0 g toluene, 4.0 g ethyl acetate anda stir bar. This solution was sealed and transferred to a dry box.Pd-1206 (0.024 g, 0.020 mmol) and DANFABA (0.048 g, 0.060 mmol) wereadded to the vessel, capped and taken out of the dry box. The desiredamount of formic acid was added. The solution was heated to 100° C. andstirred for 16 hours. The reaction mixture was then allowed to cool toroom temperature, diluted with 2 g of THF (10 g of THF for example 4a)and an analysis for molecular weight and % conversion were performed.

TABLE 4 Example % Formic Acid Conversion Mw Mw/Mn 4a 0%  98% 73100 4.184b 3%  97% 11020 1.79 4c 5%  98% 7360 1.65 4d 7%  99% 4510 1.48 4e9% >97% 4170 1.45 4f 11%  >97% 3860 1.49 4g 13%  >97% 3470 1.46 4h15%  >97% 3290 1.44

Example 5 Polymerization of TFSNB/FPCNB (75/25)

An appropriate sized reaction vessel was charged with 7.66 g (30.0 mmol)TFSNB, 2.70 g (10.0 mmol) FPCNB, 12.0 g toluene, 4.0 g ethyl acetate anda stir bar. This solution was sealed and transferred to a dry box.Pd-1206 (0.048 g, 0.040 mmol) and DANFABA (0.096 g, 0.12 mmol) wereadded to the vessel, capped and taken out of the dry box. The desiredamount of formic acid was added. The solution was heated to 100° C. andstirred for 16 hours. The reaction mixture was then allowed to cool toroom temperature and an analysis for molecular weight and conversionwere performed.

TABLE 5 Example % Formic Acid Conversion Mw Mw/Mn 5a  7% >95% 4520 1.485b  9% >95% 4180 1.47 5c 11% >95% 3620 1.49 5d 13% >95% 3220 1.43

Example 6 Polymerization of TFSNB/FPCNB/HFANB (60/20/20)

In an appropriate sized reaction vessel, TFSNB (18.4 g, 0.072 mmol),FPCNB (6.48 g, 0.024 mmol), HFANB (6.58 g, 0.0240 mmol), DANFABA (0.144g, 0.00018 mmol) were mixed with toluene (40 mL) and ethyl acetate (9ml) and added to a reaction vessel. The desired amount of formic acid(see table for details) were added. The vessel was sealed and thenheated to 100 C. The catalyst, Pd-1206 (0.072 g, 0.000060 mmol), inethyl acetate (3.9 ml) was added to the vessel. The mixture was stirredfor 16 hours. The reaction mixture was then cooled and subjected tototal solids analysis (for conversion) and GPC analysis (for molecularweight).

TABLE 6 Example % Formic Acid Conversion Mw Mw/Mn 6a  9% 100% 4100 1.516b 11% 100% 3460 1.50 6c 15% 100% 3120 1.46

Example 7 Polymerization of TFSNB/FPCNB/HFANB (20/20/60)

An appropriate sized reaction vessel, TFSNB (6.13 g, 0.024 mmol), FPCNB(6.48 g, 0.024 mmol), HFANB (19.7 g, 0.072 mmol), and DANFABA (0.144 g,0.00018 mmol) were mixed with toluene (42 mL) and ethyl acetate (9 ml)and added to the vessel. The desired amount of formic acid (see tablefor details) was added. The vessel was sealed and then heated to 100 C.The catalyst, Pd-1206 (0.072 g, 0.000060 mmol), in ethyl acetate (3.9ml) was added to the vessel. The mixture was stirred for 17 hours. Thereaction mixture was then cooled and subjected to total solids analysis(for conversion) and GPC analysis (for molecular weight).

TABLE 7 Example % Formic Acid Conversion Mw Mw/Mn 7a  9% 100% 5580 1.797b 11% 100% 5370 1.89 7c 20% 100% 3980 1.70

Example 8 Polymerization of 25/75 PhOAcNB/MeOAcNB

An appropriate sized reaction vessel, PhOAcNB (6.85 g, 0.030 mmol),MeOAcNB (15.0 g, 0.090 mmol), DANFABA (0.029 g, 0.000036 mol) andtoluene (29 mL) were mixed and added to the vessel. The desired amountof formic acid (see table for details) were added. The vessel was sealedand then heated to 100 C. The catalyst, Pd-1206 (0.014 g, 0.000012 mol),in ethyl acetate (6.4 ml) was added to the reactor. The mixture wasstirred for 18 hours. The reaction mixture was then cooled and subjectedto total solids analysis (for conversion) and GPC analysis (formolecular weight).

TABLE 8 Example % Formic Acid Conversion Mw Mw/Mn 8a 30% 100% 5070 2.838b 40% 100% 3700 2.42

Example 9 Polymerization of MeOAcNB

An appropriate sized reaction vessel, MeOAcNB (23.3 g, 0.14 mmol),DANFABA (0.034 g, 0.000042 mmol) were mixed with toluene (31 mL) andadded to the vessel. The desired amount of formic acid (see table fordetails) was added. The reactor was sealed and then heated to 100 C. Thecatalyst, Pd-1206 (0.017 g, 0.000014 mmol), in ethyl acetate (6.2 ml)was added to the vessel. The mixture was stirred for 18 hours. Thereaction mixture was then cooled and subjected to total solids analysis(for conversion), GPC analysis (for molecular weight) and MALDI-TOF MSanalysis (for end-group identification).

TABLE 9 % Formic MALDI-TOF Ex # Acid Conversion Mw Mw/Mn MS Result 9a30% DCOOH 100% 8220 3.46 D-(MeOAcNB)n-H 9b 30% HCOOD 100% 3460 2.31H-(MeOAcNB)n-D 9c 30% DCOOD 100% 8410 2.83 D-(MeOAcNB)n-D 9d 30% HCOOH100% 4090 2.51 H-(MeOAcNB)n-H

Example 10 Polymerization of TFSNB/FPCNB/HFANB (60/20/20)

The following process was used for all examples presented in Table 10except that the results for 10j, 10k and 10m were obtained from apolymerization conducted at 110° C.

An appropriated sized reaction vessel was charged with 7.66 g (36.0mmol) of TFSNB, 3.24 g (12.0 mmol) of FPCNB, 3.29 g (12.0 mmol) ofHFANB, DANFABA (0.072 g, 0.090 mmol), 15.1 g toluene and 5.83 g ethylacetate. (0.030 mmol) of the catalyst indicated in Table 10 and toluene(2.39 g) were added to a separate vessel. The desired amount of formicacid (indicated in Table 10) was added to the monomer solution in thereaction vessel and such solution was heated to 100° C. The catalystfrom the separate vessel was added to the monomer solution by syringeand allowed to react, with stirring, for about 16 hours. After cooling,a GPC analysis (for molecular weight) and total solid measurement (forconversion) were performed.

TABLE 10 % Conv Example Catalyst FA (TS) Mw Mw/Mn OD 10a Pd-1627 5 983644 1.49 0.49 10b ″ 10 100 2679 1.41 10c ″ 15 94 2481 1.38 10d Pd-17315 89 4595 1.51 0.24 10e ″ 10 96 2993 1.43 0.22 10f ″ 15 90 2789 1.43 10g″ 3 99 5440 1.59 10h ″ 5 100 4150 1.50 10i ″ 7 100 3240 1.42 10j ″ 3 995440 1.59 10k ″ 5 100 4150 1.50 10m ″ 7 100 3240 1.42

Example 11 Polymerization of TFSNB/FPCNB (75/25)

The following general process was used to form the polymers of Tables11A and 11B. For the polymers of Table 11A the catalyst employed and thepercent CTAA were varied, while for the polymers in Table 11B, only thecatalyst Pd-1627 was used, but at different monomer to catalyst ratios,different temperatures and different reaction solvents, as shown in suchtable.

An appropriate sized reaction vessel was charged with TFSNB 11.49 g(45.0 mmol), FPCNB 4.05 g (15.0 mmol), DANFABA 0.072 g (0.090 mmol) anddissolved in an appropriate amount of either toluene/ethyl acetate oftrifluorotoluene/ethyl acetate (75/25 mol %) such that the monomercharge in the vessel was about 40 wt % of the total charge. 0.030 mmolof the catalyst indicated in Table 11, below, was added to a separatevessel with toluene (3.85 g). The desired amount of formic acid wasadded to the monomer solution in the reaction vessel and the solutionwas heated to 100° C. for the experiments of Table 11A and thetemperature indicated for those shown in Table 11B. The catalyst fromthe separate vessel was added to the monomer solution by syringe and inallowed to react, with stirring, for about 16 hours. After cooling, aGPC analysis (for molecular weight) and total solid measurement (forconversion) were performed.

TABLE 11A Ex # Catalyst % FA Conversion Mw Mw/Mn OD 11a Pd-1296 9 90%7643 2.13 11b ″ 7 91% 8074 2.10 11e Pd-1348 9 76% 8820 2.10 11d ″ 7 77%9744 2.12 11e Pd-1627 5 92%. 3635 1.47 0.42 11f ″ 9 97% 2843 1.41 11g 1597% 2274 1.34 11h Pd-1731 5 87% 4536 1.52 11i ″ 9 92% 3189 1.42 0.22 11j15 100% 2486 1.39

TABLE 11B Conv Ex # Mon:Cat Temp Solvent % FA (TS) Mw Mw/Mn 11k 1500:1:3 80 75/25 5 62 11m ″ ″ Tol/EA 10 56 11n ″ ″ 15 54 11o 1000:1:3  80 ″ 574 11p ″ 10 74 11q ″ 15 71 11r 2000:1:3 100 75/25 5 97 3451 1.51 11s ″ ″TFT/EA 10 97 2718 1.42 11t ″ ″ 15 98 2314 1.39

Example 12 Polymerization of HFANB/MeOAcNB (55/45)

The following process is used for all examples in Table 12 except thatPd-1731 was used for Experiments 12a through 12f and Pd-1627 was usedfor Experiments 12g through 12i.

An appropriate sized reaction vessel was charged with 9.05 g (33.0 mmol)of HFANB, 4.49 g (27.0 mmol) of MeOACNB, (0.072 g, 0.090 mmol) ofDANFABA, 12.2 g toluene and 4.97 g ethyl acetate. An appropriate amountof the appropriate catalyst (0.030 mmol of the catalyst with the amountof monomer indicated above represents a 5000:1 monomer to catalystratio) and toluene (2.39 g) were added to a separate vessel. The desiredamount of formic acid was added to the monomer solution. The catalystfrom the separate vessel was added to the monomer solution by syringeand in allowed to react, with stirring, for from about 16 to 18 hours.After cooling, a GPC analysis (for molecular weight) and total solidmeasurement (for conversion) were performed.

TABLE 12 Ex # Mon:Cat % FA Conversion Mw Mw/Mn OD 12a 2000:1:3  5 100%6046 2.31 12b ″ 10 100% 4607 2.23 12c ″ 15 100% 3993 2.11 0.27 12d5000:1:3 15 73% 12e 10k:1:3 ″ 39% 12f 20k:1:3 ″ 16% 12g  5k:1:3 15 57%12h 10k:1:3 ″ 27% 12i 20k:1:3 ″ 13%

Catalyst Examples 1-6 illustrate the formation of some catalysts usefulin embodiments of the present invention.

Catalyst Example 1a Pd-910

A solution of (allyl)palladium(II) chloride dimer (2.21 g, 6.05 mmol)dissolved in 22 mL CH₂Cl₂ and 12 mL MeCN was added to a solution ofsilver tetrakis(pentafluorophenyl)borate (11.74 g, 12.09 mmol), 1.5 mLtoluene dissolved in 22 mL CH₂Cl₂. An immediate white precipitateformed. The solution was stirred for 20 minutes, at which point it wasfiltered through Celite® and concentrated under vacuum to form a lightyellow oil. The oil was shaken with n-pentane (2×20 mL) and dried invacuo to produce a light yellow solid. Yield: 10.2 g (93%). ¹H NMR(CD₂Cl₂, 500 MHz): δ 2.28 (s, 6H), 3.19 (d, 2H), 4.33 (d, 2H), 5.65(sept, 1H).

Catalyst Example 1b Pd-910

To a yellow solution of (allyl)palladium(II) chloride dimer (0.402 g,1.10 mmol) and LiFABA.2.5 Et₂O (1.92 g; 2.20 mmol) dissolved in 30 mLCH₂Cl₂ was added a colorless solution of silver trifluoroacetate (0.486g, 2.20 mmol) dissolved in 5 mL MeCN. A white precipitate formsimmediately. The solution is stirred for 1 h at which point it isfiltered through Celite® and concentrated under vacuum to a light yellowoil. The oil is shaken with 2×20 mL n-pentane and dried in vacuo for 30min. to produce a white solid. 1.60 g yield (80% yield). ¹H NMR (CD₂Cl₂,500 MHz): δ 2.24 (s, 6H), 3.18 (d, 2H), 4.33 (d, 2H), 5.65 (sept, 1H).¹⁹F NMR (CD₂Cl₂, 470 MHz): δ −133.9, −164.3, −168.0.

Catalyst Example 2 Pd-641

A solution of (allyl)palladium(II) chloride dimer (2.50 g, 6.82 mmol)dissolved in 10 mL CH₂Cl₂ and 10 mL MeCN was added to a solution ofsilver tris(trifluoromethylsulfonyl)methide (6.26 g, 13.6 mmol) (seeInorg. Chem. 1988, 27, 2135) dissolved in 20 mL MeCN. An immediate whiteprecipitate formed. The solution was stirred for 90 minutes, at whichpoint it was filtered through Celite® and concentrated under vacuum toform an oily solid. The oily solid was washed with 10 mL ether followedby 20 mL n-pentane and place in −5° C. freezer for 16 hrs. The solidswere collected and dry in vacuo to produce a light yellow solid. Yield5.58 g (70%). ¹H NMR (CD₂Cl₂, 500 MHz): δ 2.23 (s, 6H), 3.19 (d, 2H),4.31 (s, 2H), 5.65 (s, 1H). ¹⁹F NMR (CD₂Cl₂, 500 MHz): δ −78.5.

Catalyst Example 3[Dimethylanilinium][Tris(trifluoromethylsulfonyl)methide]

In an appropriate sized reaction vessel, 10.00 g of a 59.1 wt % solutionof (CF₃SO₃)CH in water was added. 4 mL ether was added to the vesselfollowed by a drop-wise addition of a solution of dimethylaniline (1.82mL, 14.34 mmol) dissolved in 10 mL ether over the course of 5 min. Thesolution was stirred for 20 minutes and the layers were separated. Theaqueous layer was collected and washed with ether (2×10 mL). The etherwashing were combined and the solvent was removed in vacuo to produce acolorless solid. Yield 7.66 g (100%). ₁H NMR (CD₂Cl₂, 500 MHz): δ 3.32(s, 6H, (CH₃)₂NHC₆H₅), 7.51-7.64 (m, 5H, (CH₃)₂NHC₆H₅). ₁₉F NMR (CD₂Cl₂,500 MHz): δ −77.2.

Catalyst Example 4 Lithium[tris(trifluoromethylsulfonyl)methide]

In an appropriate sized reaction vessel, 10.00 g of a 59.1 wt % solutionof (CF₃SO₃)CH in water was added. Solid lithium hydroxide (0.403 g,16.81 mmol) was added portion wise, and the solution was stirred for 10minutes as the temperature rose to ˜50° C. and returned to room temp.The solution was filtered and concentrated to dryness to produce a whitesolid. Yield 6.08 g (100%). ¹⁹F NMR (CD₂Cl₂, 500 MHz): δ −77.1.

Catalyst Example 5 Pd-967

To a yellow suspension of Pd-304 (7.56 g, 24.8 mmol) in 480 mL of a 1:1mixture of THF/MeCN was added a brown solution of LiFABA (21.6 g, 24.8mmol) dissolved in 100 mL MeCN. The mixture is stirred overnight atwhich point it is filtered through Celite® and alumina filtering aid andconcentrated under vacuum to a brown/orange solid. Yield: 22.70 g (94%).¹H NMR (CD₂Cl₂, 500 MHz): δ 2.02 (s, 6H), 2.06 (s, 6H), 5.54 (s, 1H).19F NMR (CD₂Cl₂): δ −133.1, −163.5, −167.9.

Catalyst Example 6 Pd-1115

To an orange solution of palladium(II) di-t-butylacetylacetonate (1.06g, 2.24 mmol) and LiFABA (1.96 g, 2.24 mmol) dissolved in 30 mL CH₂Cl₂was added t-BuNH₂ (0.473 mL, 4.48 mmol). The solution became a yellowsuspension over the course of 20 min. The mixture is stirred overnightat which point it is filtered through Celite® filtering aid andconcentrated under vacuum to a yellow solid. Yield: 2.06 g (82%). ¹H NMR(CD₂Cl₂, 500 MHz): δ 1.15 (s, 18H), 1.44 (s, 18H), 2.80 (s, 4H), 5.90(s, 1H).

Catalyst Example 7 Pd-917

To a mixture of tris(dibenzylideneacetone)dipalladium (0) (2.97 g, 3.24mmol), 1,4-benzoquinone (1.75 g, 16.2 mmol) and norbornene (3.05 g, 32.4mmol) was added 100 mL acetone. The solution was stirred for 30 min atambient temperature at which point the color changed from deep purple toreddish-brown. The solvent was concentrated in vacuo to ca. 20 mL and150 mL ether was added to precipitate a brown solid. The solid wascollected by cannula filtration, washed with 2×50 mL ether and dried invacuo to produce a brown solid. Yield: 0.170 g (8.5%). ¹H NMR (CDCl₃,500 MHz): δ −0.25 (2H, d), 0.44 (2H, d), 1.21 (4H, m), 1.61 (4H, m),2.95 (4H, s), 4.43 (4H, ddd), 4.78 (4H, s), 4.95 (4H, ddd).

Common to all examples that follow is that the reagents used areessentially oxygen free. That is to say that either the reagents andsolvents are charged into a reaction vessel and then sparged withnitrogen for a period of time believed sufficient to remove essentiallyall dissolved oxygen, or the reagents and solvents are individuallysparged prior to their use and stored under a nitrogen blanket prior tobeing charged to the reaction vessel. Therefore it will be understoodthat while a specific experimental description will not refer to eitherof the above methods of providing oxygen free reagents and solvents, oneor the other was performed. Further, while not specifically mentioned inevery example, an appropriate method of stirring or otherwise agitatingthe contents of a reaction vessel was provided.

Comparative Example 1 Polymerization of MeOAcNB using Pd-444

Nitrogen sparged MeOAcNB (9.97 g, 60.1 mmol) and toluene (14.96 g) werecombined in a glass vial equipped with a stirbar. In a separate vial,Pd-444 (0.0265 g, 0.0600 mmol) was dissolved in nitromethane (4 mL) andethylacetate (4 mL). To the catalyst solution was added P(n-Bu)₃ (0.0121g, 0.0600 mmol). The monomer solution was heated to 110° C. and thecatalyst solution was injected into the monomer solution. The reactionwas allowed to stir at 110° C. for 21 hours. After cooling to roomtemperature, the polymerization conversion was determined by totalsolids measurement (49%). GPC: Mw=2760, Mn=1740. The polymer solutionwas filtered to remove black palladium metal and was evaporated todryness then dissolved in a minimum of toluene. The toluene solution waspoured into hexanes (4-5 times the polymer solution volume) to form apolymer precipitate. The precipitated polymer was filtered and driedunder vacuum at 80° C. overnight. ¹H NMR (CDCl₃): δ 0.5-2.7 (br m,aliphatic hydrogens), 3.5-4.5 (br m, —CH₂—OC(O)Me), 4.7-5.0 (br s,>C═CH₂, exo-cyclic olefinic end group hydrogens), 5.6-5.9 (br m, —CH═CH—endo-cyclic olefinic end group hydrogens). MALDI-TOF MS: the majorseries of (M+Na)+ ions was observed: m/z=1849, 2015, 2181, 2347, 2513,etc. The MALDI-TOF MS and ¹H NMR data are consistent with the followingdiene end group structure, Formula X.

Comparative Example 2 Polymerization of 55/45 HFANB/MeOAcNB using Pd-444

In the glove box, MeOAcNB (4.49 g, 0.0270 mol), HFANB (9.05 g, 0.0330mol), and toluene (13.6 g) were mixed in a vial equipped with a stirbar.The vial was sealed and brought out of the dry box. The appropriateamount of formic acid was added to the vial (see Table A below). Thevial was heated to 90 C and Pd-444 (0.027 g, 0.0600 mmol) innitromethane (1.31 g) was added. The reaction mixture was stirred at 90C for 17 hours. The reaction mixture was then cooled and subjected tototal solids analysis (for conversion) and GPC analysis (for molecularweight). The reaction mixtures were purified by removal of catalystresidues. The polymers were precipitated into hexanes and driedovernight in a vacuum oven at 60 C. The OD of the precipitated polymerwas determined. The results shown in Table A show that the OD of thepolymer does not change significantly as a function of Mw (and thereforea function of formic acid concentration). Samples 2a and 2d weresubjected to MALDI-TOF MS analysis. The major series of (M+Na)⁺ ionsobserved were consistent with copolymers of HFANB and MeOAcNB with thediene end group structure shown in Formula VII. In the ¹H NMR spectra ofsamples 2a through 2d, olefinic resonances are observed from 4.7 to 5.0and 5.3 and 5.9 ppm consistent with the diene end group structure inFormula VII.

TABLE A Reaction After Comparative % Conv Mixture precipitation ODExample FA (TS) Mw Mw/Mn Mw Mw/Mn (193) 2a 0 92 5140 1.69 5470 1.57 0.552b 6 100 5140 1.71 5640 1.56 0.49 2c 12 100 4970 1.69 5440 1.63 0.50 2d18 94 4830 1.69 5090 1.63 0.55

As it is readily seen in Table A, the addition of the formic acid CTAAto a Pd-444 catalyzed polymerization mixture seems to be ineffective formolecular weight control. As theorized previously, such a resultsuggests that Pd-444 is absent a moiety that can be replaced by theCTAA.

Example 13 Polymerization of MeOAcNB with Glacial HOAc and Formic Acid

In an appropriate sized reaction vessel, MeOAcNB, (9.97 g, 0.06 mmol)was mixed with (16 mL) toluene and added to the vessel and stirred.Glacial acetic acid, (0.07 g, 0.0012 mmol) and the desired amount offormic acid (see table for details) were added. The vessel was sealedand then heated to 110° C. The catalyst, Pd-641 (0.038 g, 0.000060 mmol)in toluene (1.7 ml) was added to the vessel. The mixture was stirred for18 hours. The reaction mixture was then cooled and subjected to totalsolids analysis (for conversion) and GPC analysis (for molecularweight).

TABLE 13 Glacial HOAc % (mol % Formic % Ex # on monomer) Acid ConversionMw Mw/Mn 13a 2% 0% 97% 3020 1.67 13b 2% 10% 91% 2580 1:65

Example 14 Polymerization of MeOAcNB with Formic Acid

In an appropriate sized reaction vessel, MeOAcNB (41.6 g, 0.251 mmol),DANFABA (0.601 g, 0.00075 mmol) and toluene (66 mL) were mixed and addedto the vessel. The desired amount of formic acid (see table for details)was added. The vessel was sealed and then heated to 110° C. Thecatalyst, Pd(acac)₂ (0.076 g, 0.00025 mol), in toluene (4.2 mL) wasadded to the vessel. The mixture was stirred for 16 hours. The reactionmixture was then cooled and subjected to total solids analysis (forconversion) and GPC analysis (for molecular weight).

TABLE 14 Ex # % Formic Acid Conversion Mw Mw/Mn OD (193nm) 14a 0% 99%5440 2.40 0.62 μ⁻¹ 14b 10% 97% 2130 1.65 0.48 μ⁻¹

The polymers resulting from Examples 14a and 14b were subjected toMALDI-TOF MS analysis. (The sample (0.1 mg/mL) and dithranol(1,8,9-anthracenetriol, 0.2 mg/mL) are dissolved in THF. Sodiumtrifluoroacetate is dissolved in methanol (0.3 mg/mL), and 30 μL of thesodium trifluoroacetate solution is added to 1 mL of the samplesolution. Equal volumes (30 μL each) of the sample/sodiumtrifluoroacetate and dithranol solutions are mixed together, and 1 μL ofthis is deposited via syringe onto the stainless steel MALDI plate andallowed to dry. The instrument is a Bruker Reflex III MALDI-TOF-MS,operated in either linear or reflectron mode, with delayed ionextraction.)

For example 14a, the molecular ions observed for the major polymerseries (−70%) was consistent with a di-olefinic end group. The ¹H NMRspectrum of the polymer in example 14a exhibited two olefinic resonancesfrom ˜5.8 to ˜5.5 ppm and at ˜4.7 ppm. For example 14b, the molecularions observed for major polymer series (˜75%) was consistent with twohydrogen termini present in the polymer chain. The other polymer series(˜25%) exhibited molecular ions consistent with a di-olefinic end group.The ¹H NMR spectrum of the polymer in Example 14b exhibited the twoolefinic resonances but at lower concentration when compared to thepolymer from example 14a. The lower concentration of di-olefinic endgroups in the polymer from Example 14b is consistent with the lower ODobserved at 193 nm despite its lower molecular weight when compared tothe polymer from Example 14a.

Example 15 Polymerization of PhOAcNB/BuNB/MeOAcNB (25/30/45)

In an appropriate sized reaction vessel, PhOAcCNB (3.42 g, 0.015 mmol),BuNB (2.70 g, 0.018 mmol), MeOAcNB (4.49 g, 0.027 mmol), DANFABA (0.144g, 0.00018 mmol) were mixed with toluene (16 mL) and added to the vesseland stirred. The desired amount of formic acid (see table for details)was added. The vessel was sealed and then heated to 110 C. The catalyst,Pd(acac)₂ (0.018 g, 0.000060 mmol), in toluene (2.1 ml) was added to thevessel. The mixture was stirred for 23 hours. The reaction mixture wasthen cooled and subjected to total solids analysis (for conversion) andGPC analysis (for molecular weight).

TABLE 15 Ex # % Formic Acid Conversion Mw Mw/Mn 15a  0% 100%  8440 3.4315b 10% 98% 2820 1.95 15c 15% 99% 2600 1.86

Example 16 Polymerization of PhOAcNB/BuNB/MeOAcNB (25/30/45)

An appropriate sized reaction vessel was charged with PhOAcNB (1.87 g,8.75 mmol), BuNB (1.58 g, 10.5 mmol), MeOAcNB (2.62 g, 15.8 mmol), 5.84g toluene and stirred. The vessel was sealed. The desired amount offormic acid was added and the solution was heated to 110° C., at whichpoint a solution containing Pd-910 (0.032 g, 0.035 mmol), DANFABA (0.084g, 0.105 mmol) dissolved in 3.64 mL toluene was added to the vessel, andthe solution was stirred for 16 hours. The mixture was then allowed tocool to room temperature, and total solids analysis (for conversion) andGPC analysis (for molecular weight) were performed.

TABLE 16 Ex # % Formic Acid Conversion Mw Mw/Mn 16a  0%  96% 6240 2.6316b  5% 100% 6260 2.67 16c 10% 100% 6180 2.67 16d 20% 100% 5710 2.50 16e30% 100% 5060 2.50 16f 40%  94% 5020 2.42

Example 17 Polymerization of TFSNB/FPCNB (75/25)

An appropriate sized reaction vessel was charged with TFSNB (7.66 g,30.0 mmol), FPCNB (2.70 g, 10.0 mmol), 12.0 g toluene, and 4.0 g ethylacetate. The vessel was sealed and transferred to a dry box. Pd(acac)₂(0.024 g, 0.079 mmol) and DANFABA (0.196 g, 0.25 mmol) were added,sealed and the vessel was taken out of the dry box. To the vessel in 5a,(0.048 g, 0.08 mmol) acetic acid was added. The desired amounts offormic acid were added to the vessels in 5b, 5c and 5d and the solutionswere heated to 120° C. and stirred for 16-20 hours. The reactionmixtures were then allowed to cool to room temperature, and GPC analysis(for molecular weight and conversion) was performed.

TABLE 17 Ex # % Formic Acid Conversion Mw Mw/Mn 17a 0% 84% 3440 1.40 17b3% 94% 2780 1.33 17c 6% 94% 2520 1.31 17d 12%  94% 2240 1.27

Example 18 Polymerization of HFANB/TFSNB (80/20)

An appropriate sized reaction vessel in 6a was charged with HFANB (8.76g, 32.0 mmol), TFSNB (2.04 g, 8.0 mmol), 12.0 g toluene, 4.0 g ethylacetate and stirred. Another appropriate sized reaction vessel in 6b wascharged with HFANB (17.53 g, 64.0 mmol), TFSNB (4.08 g, 16.0 mmol), 24.0g toluene, 8.0 g ethyl acetate and stirred. These solutions were sealedand each transferred to a dry box. Pd(acac)₂ (0.024 g, 0.08 mmol) andDANFABA (0.19 g, 0.24 mmol) were added to the vessel in 6a and Pd(acac)₂(0.049 g, 0.16 mmol) and DANFABA (0.39 g, 0.48 mmol) were added to thevessel in Example 6b. The vessels were seal and each taken out of thedry box. Formic acid (0.37 g, 8.0 mmol) was added to the vessel in 6b.The solutions were heated to 115° C. and stirred for 18 hours. Thereaction mixtures were then allowed to cool to room temperature, and GPCanalysis (for molecular weight and conversion) was performed.

TABLE 18 Ex # % Formic Acid % Conversion Mw Mw/Mn 18a  0% 93% 8040 1.9718b 10% 98% 3970 1.46

Example 19 Polymerization of HFANB/TFSNB/FPCNB (75/20/5 and 80/15/5)

Appropriate sized reaction vessels in 7a and 7b was charged with HFANB(16.4 g, 60.0 mmol), TFSNB (4.08 g, 16.0 mmol), FPCNB (1.08 g, 4.0mmol), 24.0 g toluene, 8.0 g ethyl acetate and stirred. An appropriatesized reaction vessel in 7c was charged with HFANB (17.5 g, 64.0 mmol),TFSNB (3.06 g, 12.0 mmol), FPCNB (1.08 g, 4.0 mmol), 24.0 g toluene, 8.0g ethyl acetate and stirred. These solutions were sealed and eachtransferred to a dry box. Pd(acac)₂ (0.024 g, 0.079 mmol) and DANFABA(0.19 g, 0.24 mmol) were added to each reaction vessel. The vessels wereseal and each taken out of the dry box. Formic acid (0.37 g, 8.0 mmol)were added to the vessels in 7b and 7c and the solutions were heated to115° C. and stirred for 18 hours. The reaction mixtures were thenallowed to cool to room temperature, and GPC analysis (for molecularweight and conversion) was performed.

TABLE 19 Ex # % Formic Acid % Conv. Mw Mw/Mn 19a  0%  88% 6830 1.65 19b10% >95% 3740 1.43 19c 10% >95% 3580 1.11

Example 20 Polymerization of BuNB/NBC₂H₄CO₂Et (50/50)

An appropriate sized reaction vessel was charged with NBC₂H₄CO₂Et (1.0g, 5.15 mmol), BuNB (0.77 g, 5.15 mmol), 1.49 g toluene, 0.50 g ethylacetate and stirred. This solution was sealed. The desired amount offormic acid was added and the solution was heated to 110° C., at whichpoint a solution containing Pd(acac)₂ (0.0064 g, 0.02 mmol), DANFABA(0.05 g, 0.062 mmol) dissolved in 0.69 mL ethyl acetate was added to thevessel, and the solution was stirred for 16 hours. The mixture was thenallowed to cool to room temperature, and total solids analysis (forconversion) and GPC analysis (for molecular weight) were performed.

TABLE 20 Ex # % Formic Acid % Conv. Mw Mw/Mn 20a 0% 100% 13200 4.10 20b5% 100% 7710 2.82 20c 10%  100% 6120 2.29

Example 21 Polymerization of PhOAcNB

An appropriate sized reaction vessel was charged with PhOAcNB (7.5 g,35.0 mmol), 7.98 g toluene and stirred. This solution was sealed. Thedesired amount of formic acid was added and the solution was heated to110° C., at which point a solution containing Pd-910 (0.032 g, 0.035mmol), DANFABA (0.084 g, 0.105 mmol) dissolved in 3.64 mL toluene wasadded, and the solution was stirred for 16 hours. The mixture was thenallowed to cool to room temperature, and total solids analysis (forconversion) and GPC analysis (for molecular weight) were performed.

TABLE 21 Ex # % Formic Acid % Conv Mw Mw/Mn 21a  0% 100% 4600 1.75 21b10% 100% 3770 1.66 21c 20% 100% 3620 1.65 21d 40% 100% 3330 1.59

Example 22 Polymerization of HFANB/MeOAcNB (60/40)

A solution of HFANB (115.1 g, 0.42 mmol), MeOAcNB (46.5 g, 0.28 mmol),Pd(acac)₂ (0.11 g, 0.35 mmol), DANFABA (0.84 g, 1.05 mmol), 180 gtoluene, and 60 g ethyl acetate was made. This master batch was dividedinto six appropriate sized vessels having the same quantity (10A-F) andone appropriate size vessel of a different quantity (10G). The desiredamount of formic acid was added to these vessels and the mixture washeated to the desired temperature (see table) for 19 hours. The mixturewas then allowed to cool to room temperature, and total solids analysis(for conversion) and GPC analysis (for molecular weight) were carriedout on the resulting mixture. The polymer was then purified to removeresidual catalyst and then precipitated into heptane and dried in avacuum oven. The optical density of the dried polymer at 193 nm wasdetermined and molecular weight (Mw) was determined by GPC analysis bothafter polymerization and precipitation.

TABLE 22 Poly. Formic Acid % OD Ex # T(° C.) mol % on monomer Conv. Mw*Mw** (μ⁻¹) 22a 60 6.0 76 6360 6670 0.173 22b 60 12.0 97 4660 4910 0.16822g 60 18.0 86 4530 4960 0.166 22c 80 6.0 100 4500 4710 0.205 22d 8012.0 100 3710 4140 0.169 22e 100 6.0 97 3860 4120 0.268 22f 100 12.0 973380 3700 0.214 *GPC after polymerization. **GPC after precipitation.

Example 23 Polymerization of HFANB/t-BuEsNB (50/50)

In an appropriate sized reaction vessel, a solution of HFANB (6.85 g,0.025 mmol), t-BuEsNB (4.85 g, 0.025 mmol), and 18 g toluene were mixedand added to a reaction vessel. Pd(acac)₂ (0.106 g, 0.349 mmol) andDANFABA (0.841 g, 1.05 mmol) were added to the vessel. The desiredamount of formic acid was added and the mixture was heated to 115° C.for 20 hours. The mixture was then allowed to cool to room temperature,and total solids analysis (for conversion) and GPC analysis (formolecular weight) were performed.

TABLE 23 Ex # % Formic Acid % Conversion Mw Mw/Mn 23a 0 >95 2510 1.6523b 4 >95 2170 1.55 23c 8 >95 2020 1.51 23d 12 >95 1830 1.48

Example 24 Polymerization of TFSNB/FPCNB/HFANB (20/10/70)

An appropriate sized reaction vessel was charged with TFSNB (3.06 g,0.012 mmol), FPCNB (1.62 g, 0.006 mmol), HFANB (11.52 g, 0.042 mmol),DANFABA (0.144 g, 0.18 mmol), 16.2 g toluene, 6 g ethyl acetate andstirred. The desired amount of formic acid (see table) was added to thevessel. The mixture was then heated to the desired temperature (seetable) at which point Pd(acac)₂ (0.018 g, 0.06 mmol) was added to themixture with a small amount of ethyl acetate and heated for 16 hours.The reaction mixture was then allowed to cool to room temperature andtotal solids determination (for conversion) and GPC analysis (formolecular weight) was performed. Residual catalyst and monomer wasremoved from 12h and 12j. The optical densities (OD) at 193 nm of thesetwo examples are reported in the table. The composition of 12h and 12jwere 20:10:70 and 21:9:69 of TFSNB:FPCNB:HFANB, respectively, from ¹HNMR analysis.

TABLE 24 Formic Acid Temp. (mol % on % OD Ex # (° C.) monomer)Conversion Mw Mw/Mn (μ⁻¹) 24a 115 0.1 58 7170 1.63 24b 115 2 97 44201.40 24c 115 6 99 3790 1.38 24d 115 10 100 3360 1.31 24e 115 15 97 31201.27 24f 100 0.1 45 11140 1.73 24g 100 2 65 6090 1.53 24h 100 6 93 43801.38 0.22 24i 100 10 100 3680 1.35 24j 100 15 99 3570 1.34 0.18

Example 25 Polymerization of TFSNB/TFENB/MCPNB (30/30/40)

An appropriate sized reaction vessel was charged with TFSNB (3.83 g,0.015 mmol), TFENB (3.36 g, 0.015 mmol), MCPNB (4.4 g, 0.02 mmol), 17.1g of toluene and stirred. LiFABA (0.065 g, 0.075 mmol) and Pd(acac)₂(0.008 g, 0.025 mmol) was added to the vessel. The desired amount offormic acid was added and the mixture was heated for 17 hours. Thereaction mixture was then allowed to cool to room temperature and totalsolids determination (for conversion) and GPC analysis (for molecularweight) was performed.

TABLE 25 Ex # % Formic Acid % Conversion Mw Mw/Mn 25a 0 43 1860 1.39 25b3 68 1500 1.32 25c 6 70 1360 1.30 25d 9 52 1620 1.34  25e* 6 75 18201.45 *trifluorotoluene solvent

Example 26 Polymerization of BuNB

In an appropriate sized reaction vessel, a solution of BuNB (5.26 g,0.035 mmol), N,N-dimethylanilinium tris(trifluoromethylsulfonyl)methide(0.028 g, 0.053 mmol), and 6.63 g cyclohexane were placed in the vesseland stirred. The vessel was sealed and the desired amount of formic acidwas added. The solution was heated to 60° C. and Pd(acac)₂ (0.0053 g,0.018 mmol) was added in 1.2 mL toluene and stirred for 17 hours. Themixture was then cooled to room temperature and total solidsdetermination (for conversion) and GPC analysis (for molecular weight)was performed. Two of the polymers (14a and 14d) were further purifiedby removal of residual catalyst and by removal of monomer byprecipitation from hexane, dried in a vacuum oven overnight. Opticaldensity (OD) at 193 nm was determined for these two polymers.

TABLE 26 OD Ex # % Conversion % Formic Acid Mw Mw/Mn (μ−1) 26a 100 36130 2.06 0.20 26b 100 5 4900 1.84 26c 100 10 5080 1.81 26d 100 17 57801.99 0.22 26e 100 20 6700 1.98 26f 100 30 7970 2.17 26g 100 35 7790 2.1026h 100 40 8260 2.21

Example 27 Polymerization of NB

In an appropriate sized reaction vessel, a solution of NB (5.65 g, 0.06mmol), N,N-dimethylanilinium tris(trifluoromethylsulfonyl)methide (0.048g, 0.090 mmol), and 7.43 g cyclohexane were placed in the vessel andstirred. The vessel was sealed and the desired amount of formic acid wasadded. The solution was heated to 60° C. and Pd(acac)₂ (0.0091 g, 0.03mmol) was added in 1.0 mL toluene and stirred for 17 hours. The mixturewas then cooled to room temperature and total solids determination (forconversion) and GPC analysis (for molecular weight) was performed.

TABLE 27 Ex # % Conversion % Formic Acid Mw Mw/Mn 27a 100 3 2360 2.6327b 100 5 1970 2.52 27c 100 10 2010 2.68 27d 100 20 3430 3.46

Example 28 Polymerization of DecNB

In an appropriate sized reaction vessel, a solution of DecNB (8.20 g,0.0350 mol), N,N-dimethylanilinium tris(trifluoromethylsulfonyl)methide(0.028 g, 0.053 mmol), and 11.16 g cyclohexane were placed in the vesseland stirred. The vessel was sealed and the desired amount of formic acidwas added. The solution was heated to 60° C. and Pd(acac)₂ (0.0053 g,0.018 mmol) was added in 1.2 mL toluene and stirred for 17 hours. Themixture was then cooled to room temperature and total solidsdetermination (for conversion) and GPC analysis (for molecular weight)was performed.

TABLE 28 Ex # % Conversion % Formic Acid Mw Mw/Mn 28a 69 3 5110 1.55 28b82 5 3730 1.36 28c 87 10 3750 1.34 28d 82 20 4120 1.38

Example 29 Polymerization of PENB

In an appropriate sized reaction vessel, a solution of PENB (6.94 g,0.035 mmol), N,N-dimethylanilinium tris(trifluoromethylsulfonyl)methide(0.028 g, 0.053 mol), and 9.0 g cyclohexane were placed in the vesseland stirred. The vessel was sealed and the desired amount of formic acidwas added. The solution was heated to 60° C. and Pd(acac)₂ (0.0053 g,0.018 mmol) was added in 1.2 mL toluene and stirred at 60° C. for 17hours. The mixture was then cooled to room temperature and total solidsdetermination (for conversion) and GPC analysis (for molecular weight)was performed.

TABLE 29 Ex # % Conversion % Formic Acid Mw Mw/Mn 29a 91 3 3940 1.54 29b100 5 3680 1.65 29c 93 10 3060 1.56 29d 86 20 4210 1.53

Example 30 Polymerization of BuNB

In an appropriate sized reaction vessel, a solution of BuNB (5.26 g,0.035 mmol) and 6.74 g p-methane were added in the vessel and stirred.DANFABA (0.084 g, 0.105 mmol) was added to the vessel and the desiredamount of formic acid was added. The solution was heated to theappropriate temperature (see table) at which point Pd(acac)₂ (0.011 g,0.035 mmol) was added in a small amount of ethyl acetate. The mixturewas stirred at temperature for 17 hours. The mixture was then cooled toroom temperature and total solids determination (for conversion) and GPCanalysis (for molecular weight) was performed.

TABLE 30 Temp. Ex # (° C.) % Formic Acid % Conversion Mw Mw/Mn 30a 115 0% 100 12790 5.57 30b 115 10% 97 8490 3.44 30c 115 20% 93 6810 2.85 30d100  0% 99 17690 5.54 30e 100 10% 98 8630 3.08 30f 100 20% 95 7050 2.6830g 80  0% 100 34770 6.33 30h 80 10% 100 14060 3.68 30i 80 20% 97 96902.89 30j 60  0% 100 107350 8.52 30k 60 10% 100 17110 3.89 30l 60 20% 10011610 3.14

Example 31 Polymerization of NBEtCO₂Et

In an appropriate sized reaction vessel, a solution of NBEtCO₂Et (7.77g, 0.04 mmol), DANFABA (0.048 g, 0.06 mmol), and 10.8 g toluene wereadded to the vessel and stirred. The desired amount of formic acid wasadded and the solution was heated to the appropriate temperature (seetable) at which point Pd(acac)₂ (0.006 g, 0.02 mmol) was added in 0.6 gtoluene. The mixture was stirred at temperature for 18 hours. Themixture was then cooled to room temperature and total solidsdetermination (for conversion) and GPC analysis (for molecular weight)was performed. For 19g, 19h, and 19i, monomer and catalyst residues wereremoved and the polymer was precipitated from heptane and dried in avacuum oven. The optical density (OD) of the polymer was then determined(see table).

TABLE 31 Temp Formic Acid % Conv. OD Ex # (° C.) mol % on monomer (TS)Mw Mw/Mn (μ⁻¹) 31a 80 10 99 7270 2.39 31b ″ 15 97 6420 2.21 31c ″ 20 965720 2.08 31d 90 5 100 6620 2.54 31e ″ 10 97 5540 2.13 31f ″ 15 96 48401.92 31g 100  5 100 5150 2.4 0.40 31h ″ 10 98 4190 2.07 0.34 31i ″ 15 943900 1.87 0.33

Example 32 Polymerization of HFANB

In an appropriate sized reaction vessel, a solution of HFANB (11.0 g,0.04 mmol), DANFABA (0.048 g, 0.06 mmol), and 15.1 g toluene were addedto the vessel and stirred. The desired amount of formic acid was addedand the vessel was sealed and then heated to 90 C. The catalyst,Pd(acac)₂ (0.006 g, 0.02 mmol) in 1.2 g toluene was added to the vesseland stirred for 18 hours. The reaction mixture was then cooled andsubjected to total solids analysis (for conversion) and GPC analysis(for molecular weight).

TABLE 32 Ex # % Formic Acid % Conversion Mw Mw/Mn 32a 0%  74% 32030 2.9832b 5% 100% 5590 1.61 32c 10%  100% 5170 1.55

Example 33 Polymerization of HFANB

In an appropriate sized reaction vessel, a solution of HFANB (11.0 g,0.04 mmol), DANFABA (0.048 g, 0.06 mmol), and 15.1 g toluene were addedto the vessel and stirred. The desired amount of formic acid was addedand the vessel was sealed and then heated to 90 C. The catalyst,bis(tetramethylheptanedionato) palladium (II) (0.009 g, 0.02 mmol) in1.2 g toluene was added to the vessel and stirred for 18 hours. Thereaction mixture was then cooled and subjected to total solids analysis(for conversion) and GPC analysis (for molecular weight).

TABLE 33 Ex # % Formic Acid % Conversion Mw Mw/Mn 33a 0%  37% 56420 1.9733b 5% 100% 5170 1.53 33c 10%  100% 5060 1.49

Example 34 Polymerization of HFANB

In an appropriate sized reaction vessel, a solution of HFANB (11.0 g,0.04 mmol), DANFABA (0.048 g, 0.06 mmol), and 15.1 g toluene were addedto the vessel and stirred. The desired amount of formic acid was addedand the vessel was sealed and then heated to 90 C. The catalyst,bis(benzoylacetonato) palladium (II) (0.009 g, 0.02 mmol) in 1.2 gtoluene was added to vessel and stirred for 18 hours. The reactionmixture was then cooled and subjected to total solids analysis (forconversion) and GPC analysis (for molecular weight).

TABLE 34 Ex # % Formic Acid % Conversion Mw Mw/Mn 34a 0%  48% 44020 2.4134b 5% 100% 5110 1.54 34c 10%  100% 4800 1.51

Example 35 Polymerization of HFANB

In an appropriate sized reaction vessel, a solution of HFANB (11.0 g,0.04 mmol), DANFABA (0.048 g, 0.06 mmol), and 15.1 g toluene were addedto the vessel and stirred. The desired amount of formic acid was addedand the vessel was sealed and then heated to 90 C. The catalyst,Pd(CF₃COCHCOCF₃)₂ (0.010 g, 0.02 mmol) in 1.2 g toluene was added tovessel and stirred for 18 hours. The reaction mixture was then cooledand subjected to total solids analysis (for conversion) and GPC analysis(for molecular weight).

TABLE 35 Ex # % Formic Acid) % Conversion Mw Mw/Mn 35a 0% 16% 17510 1.9635b 5% 67% 15360 1.55 35c 10%  79% 14170 1.58

Example 36 Polymerization of HFANB

For 24a-i, an appropriate size reaction vessel was charged with HFANB(129.8 g, 470.0 mmol) and 195.6 g of toluene and sealed. DANFABA (2.26g, 2.82 mmol) was added to the solution. The appropriate catalyst (seetable) (0.075 mmol each) was added to 25 g portions of the abovesolution and sealed. The desired amount of formic acid was added to thesolution and heated to 100° C. and stirred for 18 hours. The reactionmixture was then allowed to cool to room temperature and GPC analysis(for molecular weight) and total solid measurement (for conversion) wereperformed.

For 24j-l, an appropriate size reaction vessel was charged with HFANB(30.2 g, 110 mmol) and 44.5 g of toluene and sealed. DANFABA (0.53 g,0.66 mmol) and Pd₂(dba)₃ (0.20 g, 0.22 mmol) were added to the vesseland separated into 25 g portions and sealed. The desired amount offormic acid (FA) was added to the 25 g portions of this solution. Thesolutions were heated to 100° C. for 17 hours. The reaction mixture wasthen allowed to cool to room temperature and GPC analysis (for molecularweight) and total solid measurement (for conversion) were performed.

TABLE 36 FA % Ex # Pd catalyst Pd catalyst (%) Conversion Mw Mw/Mn 36aPd(OAc)₂* 0.017 g 0 100 9480 2.35 36b Pd(OAc)₂ 0.017 g 5.0 100 5610 1.7136c Pd(OAc)₂ 0.017 g 10.0 100 5580 1.68 36d Pd(acac)₂** 0.023 g 0 1009960 2.28 36e Pd(acac)₂ 0.023 g 5.0 100 5540 1.68 36f Pd(acac)₂ 0.023 g10.0 100 5320 1.67 36g Pd(CF₃COCHCOCF₃)₂*** 0.039 g 0 42 13500 2.16 36hPd(CF₃COCHCOCF₃)₂ 0.039 g 5.0 81 12480 1.80 36i Pd(CF₃COCHCOCF₃)₂ 0.039g 10.0 68 10080 1.75 36j Pd₂(dba)₃**** 0.067 g 0 81 17070 2.40 36kPd₂(dba)₃ 0.067 g 5.0 100 5400 1.68 36l Pd₂(dba)₃ 0.067 g 10.0 100 56801.68 *Palladium(II) acetate. **Palladium(II) acetylacetonate,***Palladium(II) hexafluoroacetylacetonate, ****Palladium(O)dibenzylideneacetone.

Example 37 Polymerization of TFSNB/FPCNB/HFANB (60/20/20)

An appropriate sized reaction vessel was charged with TFSNB (18.4 g,72.0 mmol), FPCNB (6.48 g, 24.0 mmol), HFANB (6.59 g, 24.0 mmol), 35.0 gof toluene, 11.7 g of ethyl acetate and sealed. DANFABA (0.288 g, 0.36mmol) and Pd (OAc)₂ (0.027 g, 0.12 mmol) were added to the solution andseparated into 25 g portions and sealed. The desired amount of formicacid was added the 25 g portions of this solution. The solution washeated to 100° C. and stirred for 17 hours. The reaction mixture wasthen allowed to cool to room temperature and GPC analysis (for molecularweight) and total solid measurement (for conversion) were performed.

TABLE 37 Ex # Pd catalyst % Formic Acid % Conv. Mw Mw/Mn 37a Pd(OAc)₂ 016 9080 1.47 37b Pd(OAc)₂ 5.0 41 3660 1.33 37c Pd(OAc)₂ 10.0 44 30801.34

Example 38 Polymerization of BuNB/TESNB (90/10)

In an appropriate sized reaction vessel, BuNB (8.11 g, 0.054 mmol),TESNB (1.54 g, 0.006 mmol), N,N-dimethylaniliniumtris(trifluoromethylsulfonyl)methide (0.048 g, 0.09 mmol), and 13.4 gcyclohexane were added to the vessel and stirred. The desired amount offormic acid was added and the vessel was sealed and then heated to 60 C.The catalyst, Pd(acac)₂ (0.009 g, 0.03 mmol) in 0.9 g toluene was addedto the vessel and the mixture was stirred for 17 hours. The reactionmixture was then cooled and subjected to total solids analysis (forconversion) and GPC analysis (for molecular weight). One polymer (26c)was further purified to remove residual monomer by precipitation fromacetone and dried in a vacuum oven overnight. The composition of thedried polymer was 89:11 BuNB:TESNB by ¹H-NMR analysis.

TABLE 38 Ex # % Formic Acid % Conversion Mw Mw/Mn 38a 0% 26% 5590 1.8338b 3% 79% 3440 1.76 38c 6% 81% 3110 1.94

Example 39 Polymerization of BuNB/AGENB (90/10)

In an appropriate sized reaction vessel, BuNB (8.11 g, 0.054 mmol),AGENB (1.08 g, 0.006 mmol), N,N-dimethylaniliniumtris(trifluoromethylsulfonyl)methide (0.048 g, 0.09 mmol), and 12.8 gtoluene were added to the vessel and stirred. The desired amount offormic acid was added and the vessel was sealed and then heated to 60 C.The catalyst, Pd(acac)₂ (0.009 g, 0.03 mmol) in 0.9 g toluene was addedto the vessel and the mixture was stirred for 17 hours. The reactionmixture was then cooled and subjected to total solids analysis (forconversion) and GPC analysis (for molecular weight). One polymer (27c)was further purified to remove residual monomer by precipitation fromacetone and dried in a vacuum oven overnight. The composition of thedried polymer was 89:11 BuNB:AGENB by 1H-NMR analysis.

TABLE 39 Ex # % Formic Acid % Conversion Mw Mw/Mn 39a 0% 16% 19100 1.5239b 3% 35% 3120 2.10 39c 6% 40% 2290 1.95

Example 40 Polymerization of HFANB/MeOAcNB. (55/45)

A solution of HFANB (7.54 g, 27.5 mmol), MeOAcNB (3.74 g, 22.5 mmol),Pd-304 (0.008 g, 0.025 mmol), DANFABA (0.060 g, 0.075 mmol), 12.5 gtoluene, and 4.2 g ethyl acetate was made. The desired amount of formicacid was added to these vessels and the mixture was heated to 90 C for16 hours. The mixture was then allowed to cool to room temperature, andtotal solids analysis (for conversion) and GPC analysis (for molecularweight) were carried out on the resulting mixture. The polymer was thenpurified to remove residual catalyst and then precipitated into heptaneand dried in a vacuum oven. The optical density of the dried polymer at193 nm was determined and molecular weight (Mw) was determined by GPCanalysis before polymerization and after purification and precipitation.See Table 40 for results. The copolymers from 28a and 28b were analyzedby MALDI-TOF MS and by 1H NMR spectrometry. The major molecular ionseries in the MALDI-TOF MS was consistent with copolymers of HFANB andMeOAcNB with hydrogen end groups. Consistent with this conclusion wasthe relative absence of olefinic end groups observed in the 1H NMRspectra of 28a and 28b.

TABLE 40 After Reaction Mixture precipitation Ex # FA (%) % Conv MwMw/Mn Mw Mw/Mn OD (193) 40a 6 100 3304 1.45 4172 1.37 0.22 40b 12 1003045 1.44 3593 1.30 0.21

A 3-D plot of the effect of polymerization temperature and formic acidconcentration on optical density for polymers made according toPolymerization Examples 22 and 40 is presented in the Plot B. The plotshows that for the Pd-304 catalyst system, higher polymerizationtemperature results in a higher optical density. The FIGURE also showsthat, for the same polymerization temperature, formic acid can be usedto lower the optical density. In Plot C, Mw vs. formic acidconcentration is shown for HFANB/MeOAcNB copolymers made using Pd-444and Pd-304 at different temperatures (data from Comparative Example 2and Examples 22 and 40). The plot shows that formic acid controls themolecular weight of copolymer made using Pd-304 and produces a copolymerwith a substantially lower OD.

Example 41 Polymerization of HFANB/MeOAcNB (55/45)

A reaction vessel was charged with 68.0 g (248 mmol) of HFANB, 33.7 g(203 mmol) of MeOAcNB, 114.5 g of toluene, 38.2 g ethyl acetate, sealed,sparged with nitrogen for 30 minutes and transferred to a dry box.Pd-304 (0.034 g, 0.11 mmol) or Pd-416 (0.045 g, 0.11 mmol) added to 120g portions of the above solution. The 120 g portions of the monomerMixtures containing the catalysts were divided to 30 g portions andDANFABA (0.022 g, 0.027 mmol), LiFABA (0.024 g, 0.027 mmol),dimethylaniline (0.007 g, 0.057 mmol), t-butylamine (0.0040 g, 0.055mmol), diethylamine (0.0040 g, 0.055 mmol) and acetonitrile (0.0020 g,0.050 mmol) was added as indicated in Table 41. Formic acid (0.31 g,6.74 mmol) was added to the vials indicated and heated to 70° C. for 17hours (with the exception of vial d which was kept at RT). Total solidmeasurements were made to determine the conversion to polymers.

TABLE 41 Pd Ex # (acac)₂ Pd(t-Buacac)₂ FA T ° C. DANFABA LiFABA t-BuNH₂NEt₂H NMe₂Ph CH₃CN TS (%) conv (%) 41a 1 0 12% 70 1 0 0 0 0 0 41.2%100.0% 41b 1 0 12% 70 0 1 0 0 0 0 26.9% 67.3% 41c 1 0  0% 70 0 1 0 0 0 023.6% 59.0% 41d 1 0  0% 23 0 1 0 0 0 0 1.5% 3.8% 41e 1 0 12% 70 0 1 0 02 0 5.9% 14.8% 41f 1 0 12% 70 0 1 0 0 0 2 20.6% 51.5% 41g 1 0  0% 70 1 00 0 0 2 6.7% 16.8% 41h 1 0 12% 70 1 0 0 0 0 2 22.2% 55.5% 41i 1 0 12% 703 0 0 0 0 2 30.5% 76.3% 41j 0 1 12% 70 1 0 0 0 0 0 40.1% 100.0% 41k 0 112% 70 0 1 0 0 0 0 20.8% 52.0% 41l 0 1 12% 70 0 1 2 0 0 0 1.9% 4.8% 41m0 1 12% 70 0 1 0 2 0 0 3.3% 8.3% * monomer:Pd = 2000:1, 17 hours

Example 42 Polymerization of HFANB/MeOAcNB (55/45)

A reaction vessel was charged with 8.29 g (30.2 mmol) of HFANB, 4.11 g(24.7 mmol) of MeOAcNB, 13.7 g of toluene, 4.57 g ethyl acetate, sealed,sparged with nitrogen for 30 minutes and transferred to a dry box.LiFABA (0.024 g, 0.028 mmol), DANFABA (0.022 g, 0.028 mmol),[(t-Buacac)Pd(t-BuNH₂)₂]FABA (0.031 g, 0.028 mmol),[(t-Buacac)Pd(NEt₂H)₂]FABA (0.031 g, 0.028 mol), [(acac)Pd(CH₃CN)₂]FABA(0.027 g, 0.028 mmol) and Pd-304 (0.0085 g, 0.028 mmol) was added asindicated in Table 42. Formic acid (0.300 g, 6.52 mmol) was added to thevials indicated in the aforementioned table and heated to 70° C. for 17hours except for vials d and e which were held at RT. Total solidmeasurements were made to determine the conversion to polymers.

TABLE 42 Ex # catalyst FA T DANFABA TS (%) conv. (%) 42a[(t-Buacac)Pd(t-BuNH₂)₂]FABA 12% 70 C. 0 0.8% 2.1% 42b[(t-Buacac)Pd(HNEt₂)₂]FABA 12% 70 C. 0 0.5% 1.1% 42c[(acac)Pd(MeCN)₂]FABA 12% 70 C. 0 13.1% 32.7% 42d [(acac)Pd(MeCN)₂]FABA 0% 23 C. 0 1.2% 3.0% 42e [(acac)Pd(MeCN)₂]FABA  0% 23 C. 1 2.2% 5.5%42f [(acac)Pd(MeCN)₂]FABA  0% 70 C. 0 0.7% 1.8% 42g[(acac)Pd(MeCN)₂]FABA  0% 70 C. 1 12.5% 31.3% 42h [(acac)Pd(MeCN)₂]FABA12% 70 C. 1 35.6% 89.0% * monomer:Pd = 2000:1, 17 hours

Example 43 Polymerization of HFANB/MeOAcNB (55/45)

To a 60 ml crimp cap vial was charged with 5.28 g (19.3 mmol) HFANB,2.62 g (15.8 mmol) MeOAcNB, 0.042 g (0.053 mmol) N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, 6.6 g ethyl acetate and a stir bar.This solution was sealed and sparged with nitrogen for 40 min. Thedesired amount of formic acid was added and the solution was heated to70° C., at which point a solution containing 0.011 g (0.018 mmol)(1,4-benzoquinone)(norbornene)palladium (0) dimer, dissolved in 1.1 gethyl acetate was added, and the solution was stirred for 16 hours. Themixture was then allowed to cool to room temperature, and total solidsanalysis (for conversion) and GPC analysis (for molecular weight) wereperformed. For Example 1a, monomer and catalyst residues were removedand the polymer was precipitated from heptane and dried in a vacuumoven. The optical density (OD) of the polymer was then determined (seetable).

TABLE 43 Ex # % Formic Acid Conversion MW Mw/Mn OD 43a 10% 100% 37301.54 0.16 43b 15% 100% 2890 1.38 43c 20% 100% 2960 1.37

Example 44 Polymerization of HFANB/MeOAcNB (55/45)

In a 60 ml crimp cap vial, 9.05 g (33.0 mmol) HFANB, 4.49 g (27.0 mmol)MeOAcNB, 0.072 g (0.090 mmol) N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate and 17.2 g trifluorotoluene were addedto the vial and stirred. The desired amount of formic acid was added andthe solution was heated to 100° C., at which point a solution containing0.027 g (0.030 mmol) Pd-910, dissolved in 2.7 g trifluorotoluene wasadded, and the solution was stirred for 18 hours. The mixture was thenallowed to cool to room temperature, and total solids analysis (forconversion) and GPC analysis (for molecular weight) were performed.

TABLE 44 Ex # % Formic Acid Conversion MW Mw/Mn 44a 10% 100% 12760 2.7944b 20% 100% 10250 2.49

Example 45 Polymerization of HFANB/MeOAcNB (55/45)

For 45a and 45b, to a 60 ml crimp cap vial was charged with 5.28 g (19.3mmol) HFANB, 2.62 g (15.8 mmol) MeOAcNB, 0.168 g (0.210 mmol)N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, 4.2 g ethylacetate and a stir bar. This solution was sealed and sparged withnitrogen for 40 min. The desired amount of formic acid was added and thesolution was heated to 60° C., at which point a solution containing0.032 g (0.035 mmol) Pd-916, dissolved in 3.2 g ethyl acetate was added,and the solution was stirred for 16 hours. The mixture was then allowedto cool to room temperature, and total solids analysis (for conversion)and GPC analysis (for molecular weight) were performed. Monomer andcatalyst residues were then removed and the polymer was precipitatedfrom heptane and dried in a vacuum oven. The optical density (OD) of thepolymer was determined (see table).

For Examples 45c, 45d and 45e, to a 60 ml crimp cap vial was chargedwith 5.28 g (19.3 mmol) HFANB, 2.62 g (15.8 mmol) MeOAcNB, 0.084 g (0.11mmol) N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, 8.6 gethyl acetate and a stir bar. This solution was sealed and sparged withnitrogen for 40 min. The desired amount of formic acid was added and thesolution was heated to 70° C., at which point a solution containing0.016 g (0.017 mmol) Pd-916, dissolved in 3.2 g ethyl acetate was added,and the solution was stirred for 16 hours. The mixture was then allowedto cool to room temperature, and total solids analysis (for conversion)and GPC analysis (for molecular weight) were performed. For Examples 45dand 45e, monomer and catalyst residues were removed and the polymer wasprecipitated from heptane and dried in a vacuum oven. The opticaldensity (OD) of the polymer was then determined (see table).

TABLE 45 Temp Ex # (° C.) % Formic Acid Conversion MW Mw/Mn OD 45a 6020% 100% 4540 1.60 0.17 45b 60 30% 100% 4110 1.53 0.16 45c 70  0%  53%18250 1.90 45d 70  5% 100% 4170 1.56 0.17 45e 70 10%  96% 4020 1.53 0.16

Example 46 Polymerization of MeOAcNB

To a 60 ml crimp cap vial was charged with 5.82 g (35.0 mmol) MeOAcNB,0.168 g (0.210 mmol) N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, 6.3 g toluene and a stir bar. Thissolution was sealed and sparged with nitrogen for 40 min. The desiredamount of formic acid was added and the solution was heated to 70° C.,at which point a solution containing 0.032 g (0.035 mmol) Pd-916,dissolved in 2.1 g ethyl acetate was added, and the solution was stirredfor 16 hours. The mixture was then allowed to cool to room temperature,and total solids analysis (for conversion) and GPC analysis (formolecular weight) were performed.

TABLE 46 Ex # % Formic Acid Conversion MW Mw/Mn 46a  5% 100% 6030 2.3346b 10% 100% 3740 1.93

Example 47 Polymerization of HFIBONB

To a 60 ml crimp cap vial was charged with 6.08 g (20.0 mmol) HFIBONB,0.192 g (0.240 mmol) N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, 6.7 g toluene, 0.4 g ethyl acetateand a stir bar. This solution was sealed and sparged with nitrogen for40 min. The desired amount of formic acid was added and the solution washeated to 80° C., at which point a solution containing 0.037 g (0.040mmol) Pd-916, dissolved in 1.8 g ethyl acetate was added, and thesolution was stirred for the desired time (see table). The mixture wasthen allowed to cool to room temperature, and total solids analysis (forconversion) and GPC analysis (for molecular weight) were performed.

TABLE 47 Ex # Time % Formic Acid Conversion MW Mw/Mn 47a 16 h  0% 97%9710 2.08 47b 16 h 0.3% 100%  8550 1.81 47c 23 h 0.5% 85% 7150 1.57

Example 48 Polymerization of HFANB

To a 60-mL crimp cap vial was charged with 9.60 g (35.0 mmol) HFANB,0.084 g (0.11 mmol) N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, 7.5 g ethyl acetate and a stir bar.This solution was sealed and sparged with nitrogen for 40 min. Thedesired amount of formic acid was added and the solution was heated to90° C., at which point a solution containing 0.034 g (0.035 mmol)Pd-910, dissolved in 6.7 g ethyl acetate was added, and the solution wasstirred for 16 hours. The mixture was then allowed to cool to roomtemperature, and total solids analysis (for conversion) and GPC analysis(for molecular weight) were performed. Monomer and catalyst residueswere then removed and the polymer was precipitated from heptane anddried in a vacuum oven. The optical density (OD) of the polymer wasdetermined (see table).

TABLE 48 Ex # % Formic Acid Conversion Mw Mw/Mn OD 48a 0% 100% 7490 1.720.53 48b 5% 100% 6560 1.81 0.46

Example 49 Polymerization of MeOAcNB

To a 60-mL crimp cap vial was charged with 5.82 g (35.0 mmol) MeOAcNB,0.084 g (0.11 mmol) N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, 5.2 g ethyl acetate and a stir bar.This solution was sealed and sparged with nitrogen for 40 min. Thedesired amount of formic acid was added and the solution was heated to90° C., at which point a solution containing 0.034 g Pd-967 (0.035mmol), dissolved in 3.4 g ethyl acetate was added, and the solution wasstirred for 16 hours. The mixture was then allowed to cool to roomtemperature, and total solids analysis (for conversion) and GPC analysis(for molecular weight) were performed. Monomer and catalyst residueswere then removed and the polymer was precipitated from heptane anddried in a vacuum oven. The optical density (OD) of the polymer wasdetermined (see table).

TABLE 49 Ex # % Formic Acid Conversion Mw Mw/Mn OD 49a 2% 100% 4570 2.050.98 49b 5% 100% 3040 1.80 0.73

Example 50 Polymerization of TFSNB/FHCNB (40/60)

In a 60 ml crimp cap vial, 4.08 g (16.0 mmol) TFSNB, 9.22 g (24.0 mmol)FHCNB, 15.2 g toluene and 1.0 g ethyl acetate were added to the vial andstirred. The desired amount of formic acid was added and the solutionwas heated to 100° C., at which point a solution containing 0.073 g(0.080 mmol) Pd-910, dissolved in 3.6 g ethyl acetate was added, and thesolution was stirred for 18 hours. The mixture was then allowed to coolto room temperature, and total solids analysis (for conversion) and GPCanalysis (for molecular weight) were performed.

TABLE 50 Ex # % Formic Acid Conversion Mw Mw/Mn 50a  5% 100%  3910 1.4050b 10% 98% 3710 1.34 50c 20% 92% 3520 1.35

As shown in Comparative Example 1, polymerization using [Pd(MeCN)4](BF4)(Pd-444) results in a norbornene polymer having a diene terminal group.Comparative Example 2 demonstrates that such catalyst does not respondto a CTAA such as formic acid to provide molecular weight control of theresulting polymer. Further, Comparative Example 2 shows that the opticaldensity of said polymer is not a function of CTAA (formic acid)concentration.

Polymerization Examples 13-24 and 31-42 demonstrate the molecular weightcontrolling effect of a CTAA for the embodiments of the presentinvention. That is to say that such examples show that by increasing theconcentration of such a CTAA, the molecular weight of the resultingpolymer generally decreases.

Polymerization examples 36j-l, 43, and 47 show that in combination withPd(0) catalyst precursors, CTAA's such as formic acid control themolecular weight of the polymer and in the case of example 45, lower theOD.

Polymerization Examples 13, 38, 39, 41 and 42 are illustrative of theeffect that a CTAA such as formic acid has on the molecular weight Mwand the percent conversion where a non-phosphorus or a non-boroncontaining catalyst is employed to initiate the polymerization. InPolymerization Examples 13-19, 23, 25, 28, 29, 32-35 and 37 the effectthat a CTAA such as formic acid has optical density OD is demonstrated.Polymerization Examples 22, 24, 30 and 31 are illustrative of the effectthat the combination of CTAA concentration, and polymerizationtemperature (T ° C.) has on control of molecular weight Mw, percentconversion and optical density (OD) of the resultant polymer.Polymerization Examples 20, 21, 26, and 27 are illustrative of theeffect that formic acid has on the molecular weight Mw on thepolymerization of various norbornene-type polymers using anon-phosphorus containing catalyst when conversions are at 100 percent.Polymerization Example 36 is illustrative of the effect that formic acidhas on the molecular weight Mw and the percent conversion on thepolymerization of norbornene-type polymers using various non-phosphoruscontaining catalysts. Additionally, the polymers from PolymerizationExamples 9 and 14 were used to develop the proposed chain transfer andactivation mechanism previously described and depicted in FIG. 1.

By now it should be realized that embodiments in accordance with thepresent invention that advantageously provide for the control of themolecular weight and/or optical density of a poly(cyclic) olefin polymerhave been described and demonstrated. Such embodiments do not encompassthe previously noted deficiencies of previously known methods for thecontrol of molecular weight and optical density and as shown in theexamples above, provide excellent conversion of monomers to polymerslittle, if any, added complexity of process.

1. A method of polymerizing poly(cyclic) olefin monomers, comprising:combining a monomer composition comprising one or more poly(cyclic)olefin monomers, a palladium catalyst complex, and a chaintransfer/activating agent to form a mixture; and polymerizing themixture to form a polymer.
 2. The method of claim 1, where the chaintransfer/activating agent provides for activating the palladium catalystcomplex for forming a palladium hydride-containing moiety.
 3. The methodof claim 1, where the chain transfer/activating agent comprises an acid.4. The method of claim 3, where the acid is formic acid.
 5. The methodof claim 4, where the formic acid and the palladium catalyst complexinteract to form a palladium formate intermediate.
 6. The method ofclaim 5, where the formic acid serves as a chain transfer/activatingagent and a catalyst activating agent.
 7. The method of claim 6, wherethe catalyst complex comprises at least one phosphorous containingmoiety.
 8. A reaction mixture comprising: one or more poly(cyclic)olefin monomers; a palladium catalyst complex; an optional co-catalyst;and a chain transfer/activating agent (CTAA).
 9. The reaction mixture ofclaim 8, where the palladium catalyst complex is essentiallyphosphorous-free.
 10. The reaction mixture of claim 9, where at leastone of the one or more poly(cyclic) olefin monomers is HFANB.
 11. Thereaction mixture of claim 9, where at least one of the one or morepoly(cyclic) olefin monomers is MeOAcNB.
 12. The reaction mixture ofclaim 9, where the CTAA is formic acid.
 13. The reaction mixture ofclaim 12, further comprising an amount of CTAA that is from 1 to 25% ofthe total monomer loading to the reaction mixture.
 14. The reactionmixture of claim 12, where the one or more poly(cyclic) olefin monomersare at least two distinct types of norbornene-type monomers.